Production process for a silicon compound

ABSTRACT

The present invention provides a silicon compound represented by Formula (1) and a polymer obtained by using the same, and this makes it possible not only to obtain an organic-inorganic composite material having a distinct structure but also to control the structure of the above polymer as a molecular aggregate. 
     
       
         
         
             
             
         
       
     
     wherein R 1  is a group independently selected from hydrogen, alkyl having a carbon atom number of 1 to 40, substituted or non-substituted aryl and substituted or non-substituted arylalkyl; in this alkyl having a carbon atom number of 1 to 40, optional hydrogens may be substituted with fluorine, and optional —CH 2 — may be substituted with —O—, —CH═CH—, cycloalkylene or cycloalkenylene; in alkylene in this arylalkyl, optional hydrogens may be substituted with fluorine, and optional —CH 2 — may be substituted with —O— or —CH═CH—; and A 1  is a group having an α-haloester bond.

TECHNICAL FIELD

The present invention relates to a novel silicon compound characterizedby having a polymerization initiating ability for addition-polymerizablemonomers and a polymer obtained using the same.

RELATED ART

Polymers have come to be used in various fields not only as a generalpurpose structure-forming material but also as a value added typematerial having high-degree function and performance, and the importanceof producing high molecular materials under precise design isincreasing. Also in the field of organic-inorganic composite materialscontaining silsesquioxane as an inorganic component, it is veryimportant to create novel functional high molecular materials.

Polymers having distinct structures have to be synthesized in order toobtain such materials. A molecular property of a polymer and a propertythereof as a molecular aggregate can not precisely be analyzed if it isnot a polymer having a distinct structure, and therefore theperformances of the high molecular material can not be optimized so thatthey meet the object. However, almost all of conventionalorganic-inorganic composite materials have not contained organicpolymers having a controlled structure. A large part of them is obtainedby mechanically blending silsesquioxane with organic polymers, andtherefore it has been very difficult to control a structure thereof as amolecular aggregate of a complex.

Then, it has come to be tried to control a structure of a polymer byusing a polymerization initiator. It is disclose in Document 1 that anα-haloester group is a good initiator for styrene base monomers andmethacrylic acid base monomers in living radical polymerization.However, silsesquioxane derivatives having an α-haloester group have notso far been known up to now. It is disclose in Document 2 thatsilsesquioxane derivatives having a chloromethylphenethyl group arerelatively good initiators for styrene base monomers in living radicalpolymerization.

Document 1: Chem. Rev., 101, 2921 to 2990 (2001)

Document 2: Chem. Mater., 13, 3436 to 3448 (2001)

An object of the present invention is to provide a novel siliconcompound having a living radical polymerization initiating ability foraddition-polymerizable monomers of a wide range and a polymer obtainedusing the same to thereby solve the problems described above regardingconventional organic-inorganic composite materials.

DISCLOSURE OF THE INVENTION

The present inventors have found a novel silsesquioxane derivativehaving an α-haloester group as a functional group.

They have found that the above compound is effective as a means forsolving the problems described above. That is, the present inventioncomprises the following structures.

[1] A silicon compound represented by Formula (1):

wherein R¹ is a group independently selected from hydrogen, alkyl havinga carbon atom number of 1 to 40, substituted or non-substituted aryl andsubstituted or non-substituted arylalkyl; in this alkyl having a carbonatom number of 1 to 40, optional hydrogens may be substituted withfluorine, and optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene; in alkylene in this arylalkyl,optional hydrogens may be substituted with fluorine, and optional —CH₂—may be substituted with —O— or —CH═CH—; and A¹ is a group having anα-haloester bond.[2] The silicon compound as described in the item [1], wherein R¹ is agroup independently selected from hydrogen and alkyl having a carbonatom number of 1 to 30 in which optional hydrogens may be substitutedwith fluorine and in which optional —CH₂— may be substituted with —O— orcycloalkylene.[3] The silicon compound as described in the item [1], wherein R¹ is agroup independently selected from alkenyl having a carbon atom number of1 to 20 in which optional hydrogens may be substituted with fluorine andin which optional —CH₂— may be substituted with —O— or cycloalkylene andalkyl having a carbon atom number of 1 to 20 in which optional hydrogensmay be substituted with fluorine and in which at least one —CH₂— issubstituted with cycloalkenylene.[4] The silicon compound as described in the item [1], wherein R¹ is agroup independently selected from non-substituted naphthyl and phenyl inwhich optional hydrogens may be substituted with halogen or alkyl havinga carbon atom number of 1 to 10; and in the alkyl which is a substituentfor the phenyl, optional hydrogens may be substituted with fluorine, andoptional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orphenylene.[5] The silicon compound as described in the item [1], wherein R¹ is agroup independently selected from phenylalkyls constituted from phenylin which optional hydrogens may be substituted with halogen or alkylhaving a carbon atom number of 1 to 12 and alkylene having a carbon atomnumber of 1 to 12 in which optional hydrogens may be substituted withfluorine and in which optional —CH₂— may be substituted with —O— or—CH═CH—; and in the alkyl which is a substituent for the phenyl,optional hydrogens may be substituted with fluorine, and optional —CH₂—may be substituted with —O—, —CH═CH—, cycloalkylene or phenylene.[6] The silicon compound as described in the item [1], wherein R¹ is agroup independently selected from alkyl having a carbon atom number of 1to 8 in which optional hydrogens may be substituted with fluorine and inwhich optional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkyleneor cycloalkenylene, phenyl in which optional hydrogens may besubstituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O— or —CH═CH—.[7] The silicon compound as described in the item [1], wherein all R¹'sare the same group selected from alkyl having a carbon atom number of 1to 8 in which optional hydrogens may be substituted with fluorine and inwhich optional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkyleneor cycloalkenylene, phenyl in which optional hydrogens may besubstituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O— or —CH═CH—.[8] The silicon compound as described in the item [1], wherein all R¹'sare the same group selected from phenyl in which optional hydrogens maybe substituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O—.[9] The silicon compound as described in the item [1], wherein all R¹'sare the same group selected from ethyl, 2-methylpropyl,2,4,4-trimethylpentyl, cyclopentyl, cyclohexyl, non-substituted phenyl,3,3,3-trifluoropropyl and tridecafluoro-1,1,2,2-tetrahydrooctyl.[10] The silicon compound as described in the item [1], wherein all R¹'sare the same group selected from non-substituted phenyl and3,3,3-trifluoropropyl.[11] The silicon compound as described in the item [1], wherein inFormula (1), R¹ is a group independently selected from hydrogen, alkylhaving a carbon atom number of 1 to 40, substituted or non-substitutedaryl and substituted or non-substituted arylalkyl; in this alkyl havinga carbon atom number of 1 to 40, optional hydrogens may be substitutedwith fluorine, and optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene; in alkylene in this arylalkyl,optional hydrogens may be substituted with fluorine, and optional —CH₂—may be substituted with —O— or —CH═CH—; and A¹ is a group represented byFormula (2):

in Formula (2), X¹ is halogen; R² is alkyl having a carbon atom numberof 1 to 20, aryl having a carbon atom number of 6 to 20 or aralkylhaving a carbon atom number of 7 to 20; R³ is hydrogen, alkyl having acarbon atom number of 1 to 20, aryl having a carbon atom number of 6 to20 or aralkyl having a carbon atom number of 7 to 20; Z¹ is alkylenehaving a carbon atom number of 1 to 20 or alkenylene having a carbonatom number of 3 to 8; and in these alkylene and alkenylene, optional—CH₂— may be substituted with —O—.[12] The silicon compound as described in the item [11], wherein R¹ is agroup independently selected from hydrogen and alkyl having a carbonatom number of 1 to 30 in which optional hydrogens may be substitutedwith fluorine and in which optional —CH₂— may be substituted with —O— orcycloalkylene.[13] The silicon compound as described in the item [11], wherein R¹ is agroup independently selected from alkenyl having a carbon atom number of1 to 20 in which optional hydrogens may be substituted with fluorine andin which optional —CH₂— may be substituted with —O— or cycloalkylene andalkyl having a carbon atom number of 1 to 20 in which optional hydrogensmay be substituted with fluorine and in which at least one —CH₂— issubstituted with cycloalkenyl.[14] The silicon compound as described in the item [11], wherein R¹ is agroup independently selected from non-substituted naphthyl and phenyl inwhich optional hydrogens may be substituted with halogen or alkyl havinga carbon atom number of 1 to 10; and in the alkyl which is a substituentfor the phenyl, optional hydrogens may be substituted with fluorine, andoptional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkylene orphenylene.[15] The silicon compound as described in the item [11], wherein R¹ is agroup independently selected from phenylalkyls constituted from phenylin which optional hydrogens may be substituted with halogen or alkylhaving a carbon atom number of 1 to 12 and alkylene having a carbon atomnumber of 1 to 12 in which optional hydrogens may be substituted withfluorine and in which optional —CH₂— may be substituted with —O— or—CH═CH—; and in the alkyl which is a substituent for the phenyl,optional hydrogens may be substituted with fluorine, and optional —CH₂—may be substituted with —O—, —CH═CH—, cycloalkylene or phenylene.[16] The silicon compound as described in the item [11], wherein R¹ is agroup independently selected from alkyl having a carbon atom number of 1to 8 in which optional hydrogens may be substituted with fluorine and inwhich optional —CH₂— may be substituted with —O—, —CH═CH—, cycloalkyleneor cycloalkenylene, phenyl in which optional hydrogens may besubstituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O— or —CH═CH—.[17] The silicon compound as described in the item [11], wherein allR¹'s are the same group selected from alkyl having a carbon atom numberof 1 to 8 in which optional hydrogens may be substituted with fluorineand in which optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene, phenyl in which optional hydrogens maybe substituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O— or —CH═CH—.[18] The silicon compound as described in the item [11], wherein allR¹'s are the same group selected from phenyl in which optional hydrogensmay be substituted with halogen, methyl or methoxy, non-substitutednaphthyl and phenylalkyl constituted from phenyl in which optionalhydrogens may be substituted with fluorine, alkyl having a carbon atomnumber of 1 to 4, vinyl or methoxy and alkylene which has a carbon atomnumber of 1 to 8 and in which optional —CH₂— may be substituted with—O—.[19] The silicon compound as described in the item [11], wherein allR¹'s are the same group selected from ethyl, 2-methylpropyl,2,4,4-trimethylpentyl, cyclopentyl, cyclohexyl, non-substituted phenyl,3,3,3-trifluoropropyl and tridecafluoro-1,1,2,2-tetrahydrooctyl.[20] The silicon compound as described in the item [11], wherein allR¹'s are the same group selected from non-substituted phenyl and3,3,3-trifluoropropyl.[21] The silicon compound as described in the item [11], wherein Z¹ isalkylene which has a carbon atom number of 1 to 20 and in which optional—CH₂— may be substituted with —O—.[22] The silicon compound as described in the item [11], wherein Z¹ is—C₂H₄—O—C₃H₆—, —C₃H₆— or —C₂H₁—; R² is methyl or ethyl; R³ is hydrogen,methyl or ethyl; and X¹ is bromine.[23] The silicon compound as described in the item [11], wherein Z¹ is—C₃H₆— or —C₂H₄—; both of R² and R³ are methyl; and X¹ is bromine.[24] A production process for the silicon compound represented byFormula (1) as described in the item [1], characterized by reacting acompound represented by Formula (3) with acid halide having ahalogenated alkyl group:

wherein R¹ is a group independently selected from hydrogen, alkyl havinga carbon atom number of 1 to 40, substituted or non-substituted aryl andsubstituted or non-substituted arylalkyl; in this alkyl having a carbonatom number of 1 to 40, optional hydrogens may be substituted withfluorine, and optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene; in alkylene in this arylalkyl,optional hydrogens may be substituted with fluorine, and optional —CH₂—may be substituted with —O— or —CH═CH—; and A² is an organic grouphaving a hydroxyl group at an end.[25] A production process for a silicon compound represented by Formula(6), characterized by reacting a compound represented by Formula (4)with a compound represented by Formula (5):

wherein all R¹²'s are the same group selected from alkyl having a carbonatom number of 1 to 8 in which optional hydrogens may be substitutedwith fluorine and in which optional —CH₂— may be substituted with —O—,—CH═CH—, cycloalkylene or cycloalkenylene, phenyl in which optionalhydrogens may be substituted with halogen, methyl or methoxy,non-substituted naphthyl and phenylalkyl constituted from phenyl inwhich optional hydrogens may be substituted with fluorine, alkyl havinga carbon atom number of 1 to 4, vinyl or methoxy and alkylene which hasa carbon atom number of 1 to 8 and in which optional —CH₂— may besubstituted with —O—; Z¹ is alkylene having a carbon atom number of 1 to20 or alkenylene having a carbon atom number of 3 to 8, and in thesealkylene and alkenylene, optional —CH₂— may be substituted with —O—;

wherein both of X¹ and X² are halogens and may be the same or different;R² is alkyl having a carbon atom number of 1 to 20, aryl having a carbonatom number of 6 to 20 or aralkyl having a carbon atom number of 7 to20; and R³ is hydrogen, alkyl having a carbon atom number of 1 to 20,aryl having a carbon atom number of 6 to 20 or aralkyl having a carbonatom number of 7 to 20;

wherein R¹ and Z¹ each have the same meanings as those of these codes inFormula (4), and R², R³ and X¹ each have the same meanings as those ofthese codes in Formula (5).[26] A polymer obtained by polymerizing an addition-polymerizablemonomer using the silicon compound as described in the item [1] as aninitiator and using a transition metal complex as a catalyst.[27] A polymer obtained by polymerizing an addition-polymerizablemonomer using the silicon compound as described in the item [11] as aninitiator and using a transition metal complex as a catalyst.[28] A polymer represented by Formula (7):

wherein all R¹²'s are the same group selected from alkyl having a carbonatom number of 1 to 8 in which optional hydrogens may be substitutedwith fluorine and in which optional —CH₂— may be substituted with —O—,—CH═CH—, cycloalkylene or cycloalkenylene, phenyl in which optionalhydrogens may be substituted with halogen, methyl or methoxy,non-substituted naphthyl and phenylalkyl constituted from phenyl inwhich optional hydrogens may be substituted with fluorine, alkyl havinga carbon atom number of 1 to 4, vinyl or methoxy and alkylene which hasa carbon atom number of 1 to 8 and in which optional —CH₂— may besubstituted with —O—; Z¹ is alkylene having a carbon atom number of 1 to20 or alkenylene having a carbon atom number of 3 to 8, and in thesealkylene and alkenylene, optional —CH₂— may be substituted with —O—; R²is alkyl having a carbon atom number of 1 to 20, aryl having a carbonatom number of 6 to 20 or aralkyl having a carbon atom number of 7 to20; R³ is hydrogen, alkyl having a carbon atom number of 1 to 20, arylhaving a carbon atom number of 6 to 20 or aralkyl having a carbon atomnumber of 7 to 20; X¹ is halogen; and P¹ is a chain of a structural unitobtained by polymerizing an addition-polymerizable monomer.[29] The polymer as described in the item [27], wherein theaddition-polymerizable monomer is at least one selected from(meth)acrylic acid derivatives and styrene derivatives.[30] The polymer as described in the item [28], wherein all R¹²'s arethe same group selected from phenyl in which optional hydrogens may besubstituted with halogen, methyl or methoxy, non-substituted naphthyland phenylalkyl constituted from phenyl in which optional hydrogens maybe substituted with fluorine, alkyl having a carbon atom number of 1 to4, vinyl or methoxy and alkylene which has a carbon atom number of 1 to8 and in which optional —CH₂— may be substituted with —O—; Z¹ is —C₃H₆—or —C₂H₄—; R² is methyl or ethyl; R³ is hydrogen, methyl or ethyl; X¹ isbromine; and P¹ is a chain of a structural unit obtained by polymerizingat least one compound selected from (meth)acrylic acid derivatives andstyrene derivatives.[31] The polymer as described in the item [28], wherein all R¹²'s arethe same group selected from ethyl, 2-methylpropyl,2,4,4-trimethylpentyl, cyclopentyl, cyclohexyl, non-substituted phenyl,3,3,3-trifluoropropyl and tridecafluoro-1,1,2,2-tetrahydrooctyl; Z¹ is—C₃H₆— or —C₂H₄—; both of R² and R³ are methyl; X¹ is bromine; and P¹ isa chain of a structural unit obtained by polymerizing at least onecompound selected from (meth)acrylic acid derivatives and styrenederivatives.[32] The polymer as described in the item [31], wherein P¹ is a chain ofa structural unit obtained by polymerizing at least one compoundselected from the styrene derivatives.

First, terms used in the present invention shall be explained. All ofalkyl, alkylene, alkenyl and alkenylene may be either linear groups orbranched groups. Both of cycloalkyl and cycloalkenyl may be or may notbe groups having a cross-linked ring structure.

“Optional” used in the present invention shows that not only theposition but also the number can optionally be selected. For example,alkyl in which optional —CH₂— may be substituted with —O— or —CH═CH— isany of alkyl, alkoxyalkyl, alkenyl, alkyloxyalkenyl, alkenyloxyalkyl andalkenyloxyalkenyl. In the present invention, however, a case where —CH₂—bonded to an ester group is substituted with —O— and a case where pluralcontinuous —CH₂— are substituted with —O— are not included.

(Meth)acrylic acid is a general term for acrylic acid and methacrylicacid. (Meth)acrylate is a general term for acrylate and methacrylate.(Meth)acryloyloxy is a general term for acryloyloxy and methacryloyloxy.

The compound represented by Formula (1) shall be described as thecompound (1). The compounds represented by the other formulas shall bedescribed by the same abbreviation.

The silicon compound of the present invention is represented by Formula(1):

In Formula (1), R¹ is a group independently selected respectively fromhydrogen, alkyl, substituted or non-substituted aryl and substituted ornon-substituted arylalkyl.

All R¹'s are preferably the same one group but may be constituted fromdifferent two or more groups. The examples of a case where seven R¹'sare constituted from different groups are a case where they areconstituted from two or more alkyls, a case where they are constitutedfrom two or more aryls, a case where they are constituted from two ormore aralkyls, a case where they are constituted from hydrogen and atleast one aryl, a case where they are constituted from at least onealkyl and at least one aryl, a case where they are constituted from atleast one alkyl and at least one aralkyl and a case where they areconstituted from at least one aryl and at least one aralkyl. They may becombinations other than the above cases. The compound (1) having atleast two different R¹'s can be obtained by using two or more rawmaterials when producing it. These raw materials shall be describedlater.

When R¹ is alkyl, it has a carbon atom number of 1 to 40.

The preferred carbon atom number is 1 to 30. The more preferred carbonatom number is 1 to 8. Optional hydrogens thereof may be substitutedwith fluorine, and optional —CH₂— may be substituted with —O—, —CH═CH—,cycloalkylene or cycloalkenylene. The preferred examples of such alkylare non-substituted alkyl having a carbon atom number of 1 to 30,alkoxyalkyl having a carbon atom number of 2 to 30, a group in which one—CH₂— is substituted with cycloalkylene in alkyl having a carbon atomnumber of 1 to 8, alkenyl having a carbon atom number of 2 to 20,alkenyloxyalkenyl having a carbon atom number of 2 to 20,alkyloxyalkenyl having a carbon atom number of 2 to 20, a group in whichone —CH₂— is substituted with cycloalkenylene in alkyl having a carbonatom number of 1 to 8 and groups in which optional hydrogens aresubstituted with fluorine in these groups given above. The preferredcarbon atom numbers of cycloalkylene and cycloalkenylene are 3 to 8.

The examples of the non-substituted alkyl having a carbon atom number of1 to 30 are methyl, ethyl, propyl, 1-methylethyl, butyl, 2-methylpropyl,1,1-dimethylethyl, pentyl, hexyl, 1,1,2-trimethylpropyl, heptyl, octyl,2,4,4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, tetradecyl,hexadecyl, octadecyl, eicosyl, docosyl and triacontyl.

The examples of the fluorinated alkyl having a carbon atom number of 1to 30 are 3,3,3-trifluoropropyl, 3,3,4,4,5,5,6,6,6-nonadecafluorohexyl,tridecafluoro-1,1,2,2-tetrahydrooctyl,heptadecafluoro-1,1,2,2-tetrahydrodecyl, perfluoro-1H,1H,2H,2H-dodecyland perfluoro-1H,1H,2H,2H-tetradecyl.

The examples of the alkoxyalkyl having a carbon atom number of 2 to 29are 3-methoxypropyl, methoxyethoxyundecyl and3-heptafluoroisopropoxypropyl.

The examples of the group in which one —CH₂— is substituted withcycloalkylene in alkyl having a carbon atom number of 1 to 8 arecyclohexylmethyl, adamantaneethyl, cyclopentyl, cyclohexyl,2-bicycloheptyl and cyclooctyl. Cyclohexyl is an example in which —CH₂—in methyl is substituted with cyclohexylene. Cyclohexylmethyl is anexample in which —CH₂— in a β position of ethyl is substituted withcyclohexylene.

The examples of the alkenyl having a carbon atom number of 2 to 20 arevinyl, 2-propenyl, 3-butenyl, 5-hexenyl, 7-octenyl, 10-undecenyl and21-docosenyl.

The example of the alkenyloxyalkyl having a carbon atom number of 2 to20 is allyloxyundecyl.

The examples of the group in which one —CH₂— is substituted withcycloalkenylene in alkyl having a carbon atom number of 1 to 8 are2-(3-cyclohexenyl)ethyl, 5-(bicycloheptenyl)ethyl, 2-cyclopentenyl,3-cyclohexenyl, 5-norbornene-2-yl and 4-cyclooctenyl.

The examples of a case where R¹ in Formula (1) is substituted ornon-substituted aryl are phenyl in which optional hydrogens may besubstituted with halogen or alkyl having a carbon atom number of 1 to 10and non-substituted naphthyl. The preferred examples of halogen are afluorine atom, a chlorine atom and bromine. In the alkyl having a carbonatom number of 1 to 10, optional hydrogens may be substituted withfluorine, and optional —CH₂— may be substituted with —O—, —CH═CH— orphenylene. That is, the preferred examples of the case where R¹ issubstituted or non-substituted aryl are non-substituted phenyl,non-substituted naphthyl, alkylphenyl, alkyloxyphenyl, alkenylphenyl,phenyl having as a substituent, a group in which optional —CH₂— in thealkyl having a carbon atom number of 1 to 10 is substituted withphenylene and groups in which optional hydrogens are substituted withhalogen in these groups.

The examples of the halogenated phenyl are pentafluorophenyl,4-chlorophenyl and 4-bromophenyl.

The examples of the alkylphenyl are 4-methylphenyl, 4-ethylphenyl,4-propylphenyl, 4-butylphenyl, 4-pentylphenyl, 4-heptylphenyl,4-octylphenyl, 4-nonylphenyl, 4-decylphenyl, 2,4-dimethylphenyl,2,4,6-trimethylphenyl, 2,4,6-triethylphenyl, 4-(1-methylethyl)phenyl,4-(1,1-dimethylethyl)phenyl, 4-(2-ethylhexyl)phenyl and2,4,6-tris(1-methylethyl)phenyl.

The examples of the alkyloxyphenyl are (4-methoxy)phenyl,(4-ethoxy)phenyl, (4-propoxy)phenyl, (4-butoxy)phenyl,(4-pentyloxy)phenyl, (4-heptyloxy)phenyl, (4-decyloxy)phenyl,(4-octadecyloxy)phenyl, 4-(1-methylethoxy)phenyl,4-(2-methylpropoxy)phenyl and 4-(1,1-dimethylethoxy)phenyl. The examplesof the alkenylphenyl are 4-vinylphenyl, 4-(1-methylvinyl)phenyl and4-(3-butenyl)phenyl.

The examples of the phenyl having as a substituent, a group in whichoptional —CH₂— in the alkyl having a carbon atom number of 1 to 10 issubstituted with phenylene are 4-(2-phenylvinyl)phenyl, 4-phenoxyphenyl,3-(phenylmethyl)phenyl, biphenyl and terphenyl. 4-(2-Phenylvinyl)phenylis an example in which one —CH₂— in ethyl of ethylphenyl is substitutedwith phenylene and in which the other —CH₂— is substituted with —CH═CH—.

The examples of the phenyl in which a part of hydrogens on a benzenering is substituted with halogen and in which the other hydrogens aresubstituted with alkyl, alkyloxy or alkenyl are 3-chloro-4-methylphenyl,2,5-dichloro-4-methylphenyl, 3,5-dichloro-4-methylphenyl,2,3,5-trichloro-4-methylphenyl, 2,3,6-trichloro-4-methylphenyl,3-bromo-4-methylphenyl, 2,5-dibromo-4-methylphenyl,3,5-dibromo-4-methylphenyl, 2,3-difluoro-4-methylphenyl,3-chloro-4-methoxyphenyl, 3-bromo-4-methoxyphenyl,3,5-dibromo-4-methoxyphenyl, 2,3-difluoro-4-methoxyphenyl,2,3-difluoro-4-ethoxyphenyl, 2,3-difluoro-4-propoxyphenyl and4-vinyl-2,3,5,6-tetrafluorophenyl.

Next, the examples of a case where R¹ in Formula (1) is substituted ornon-substituted arylalkyl shall be given. In alkylene of the arylalkylconstituting the arylalkyl, optional hydrogens may be substituted withfluorine, and optional —CH₂— may be substituted with —O— or —CH═CH—. Thepreferred example of the arylalkyl is phenylalkyl. In this case, thepreferred carbon atom number of the alkylene is 1 to 12, and the morepreferred carbon atom number is 1 to 8. The examples of thenon-substituted phenylalkyl are phenylmethyl, 2-phenylethyl,3-phenylpropyl, 4-phenylbutyl, 5-phenylpentyl, 6-phenylhexyl,11-phenylundecyl, 1-phenylethyl, 2-phenylpropyl, 1-methyl-2-phenylethyl,1-phenylpropyl, 3-phenylbutyl, 1-methyl-3-phenylpropyl, 2-phenylbutyl,2-methyl-2-phenylpropyl and 1-phenylhexyl.

In the phenylalkyl, optional hydrogens on a benzene ring may besubstituted with halogen or alkyl having a carbon atom number of 1 to12. In this alkyl having a carbon atom number of 1 to 12, optionalhydrogens may be substituted with fluorine, and optional —CH₂— may besubstituted with —O—, —CH═CH—, cycloalkylene or phenylene. The examplesof the phenylalkyl in which optional hydrogens on phenyl are substitutedwith fluorine are 4-fluorophenylmethyl,2,3,4,5,6-pentafluorophenylmethyl, 2-(2,3,4,5,6-pentafluorophenyl)ethyl,3-(2,3,4,5,6-pentafluorophenyl)propyl, 2-(2-fluorophenyl)propyl and2-(4-fluorophenyl)propyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with chlorine are 4-chlorophenylmethyl,2-chlorophenylmethyl, 2,6-dichlorophenylmethyl,2,4-dichlorophenylmethyl, 2,3,6-trichlorophenylmethyl,2,4,6-trichlorophenylmethyl, 2,4,5-trichlorophenylmethyl,2,3,4,6-tetrachloro-phenylmethyl, 2,3,4,5,6-pentachlorophenylmethyl,2-(2-chlorophenyl)ethyl, 2-(4-chlorophenyl)ethyl,2-(2,4,5-chlorophenyl)ethyl, 2-(2,3,6-chlorophenyl)ethyl,3-(3-chlorophenyl)propyl, 3-(4-chlorophenyl)propyl,3-(2,4,5-trichlorophenyl)propyl, 3-(2,3,6-trichlorophenyl)propyl,4-(2-chlorophenyl)butyl, 4-(3-chlorophenyl)butyl,4-(4-chlorophenyl)butyl, 4-(2,3,6-trichlorophenyl)butyl,4-(2,4,5-trichlorophenyl)butyl, 1-(3-chlorophenyl)-ethyl,1-(4-chlorophenyl)ethyl, 2-(4-chlorophenyl)-propyl,2-(2-chlorophenyl)propyl and 1-(4-chlorophenyl)butyl.

The examples of the phenylalkyl in which hydrogens on phenyl aresubstituted with bromine are 2-bromophenylmethyl, 4-bromophenylmethyl,2,4-dibromophenylmethyl, 2,4,6-tribromophenylmethyl,2,3,4,5-tetrabromophenylmethyl, 2,3,4,5,6-pentabromophenylmethyl,2-(4-bromophenyl)ethyl, 3-(4-bromophenyl)propyl,3-(3-bromophenyl)propyl, 4-(4-bromophenyl)butyl, 1-(4-bromophenyl)ethyl,2-(2-bromophenyl)propyl and 2-(4-bromophenyl)propyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 are2-methylphenylmethyl, 3-methylphenylmethyl, 4-methylphenylmethyl,4-dodecylphenylmethyl, 3,5-dimethylphenylmethyl,2-(4-methylphenyl)ethyl, 2-(3-methylphenyl)ethyl,2-(2,5-dimethylphenyl)ethyl, 2-(4-ethylphenyl)ethyl,2-(3-ethylphenyl)ethyl, 1-(4-methylphenyl)ethyl,1-(3-methylphenyl)ethyl, 1-(2-methylphenyl)ethyl,2-(4-methylphenyl)propyl, 2-(2-methylphenyl)propyl,2-(4-ethylphenyl)propyl, 2-(2-ethylphenyl)propyl,2-(2,3-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)propyl,2-(3,5-dimethylphenyl)-propyl, 2-(2,4-dimethylphenyl)propyl,2-(3,4-dimethylphenyl)propyl, 2-(2,5-dimethylphenyl)butyl,(4-(1-methylethyl)phenyl)methyl, 2-(4-(1,1-dimethylethyl)phenyl)ethyl,2-(4-(1-methylethyl)-phenyl)propyl and2-(3-(1-methylethyl)phenyl)propyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 and inwhich hydrogens in this alkyl are substituted with fluorines are3-(trifluoromethyl)phenylethyl, 2-(4-trifluoromethylphenyl)ethyl,2-(4-nonafluorobutyl-phenyl)ethyl, 2-(4-tridecafluorohexylphenyl)ethyl,2-(4-heptadecafluorooctylphenyl)ethyl, 1-(3-trifluoromethylphenyl)ethyl,1-(4-trifluoromethyl-phenyl)ethyl, 1-(4-nonafluorobutylphenyl)ethyl,1-(4-tridecafluorohexylphenyl)ethyl,1-(4-heptadecafluorooctylphenyl)ethyl,2-(4-nonafluorobutylphenyl)propyl,1-methyl-1-(4-nonafluorobutylphenyl)ethyl,2-(4-tridecafluorohexyl-phenyl)propyl,1-methyl-1-(4-tridecafluorohexyl-phenyl)ethyl,2-(4-heptadecafluorooctylphenyl)propyl and1-methyl-1-(4-heptadecafluorooctylphenyl)ethyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 and inwhich —CH₂— in this alkyl is substituted with —CH═CH— are2-(4-vinylphenyl)ethyl, 1-(4-vinylphenyl)ethyl and1-(2-(2-propenyl)phenyl)ethyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 and inwhich —CH₂— in this alkyl is substituted with —O— are4-methoxyphenylmethyl, 3-methoxyphenylmethyl, 4-ethoxyphenylmethyl,2-(4-methoxyphenyl)ethyl, 3-(4-methoxyphenyl)propyl,3-(2-methoxyphenyl)propyl, 3-(3,4-dimethoxyphenyl)propyl,11-(4-methoxyphenyl)undecyl, 1-(4-methoxyphenyl)ethyl,2-(3-(methoxymethyl)phenyl)ethyl and3-(2-nonadecafluorodecenyloxyphenyl)propyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 and inwhich one of —CH₂— in this alkyl is substituted with cycloalkylene are,to give examples thereof including a case where another —CH₂— issubstituted with —O—, cyclopentylphenylmethyl,cyclopentyloxyphenylmethyl, cyclohexylphenylmethyl,cyclohexylphenylethyl, cyclohexylphenylpropyl andcyclohexyloxyphenylmethyl.

The examples of the phenylalkyl in which hydrogens on a benzene ring aresubstituted with alkyl having a carbon atom number of 1 to 12 and inwhich one of —CH₂— in this alkyl is substituted with phenylene are, togive examples thereof including a case where another —CH₂— issubstituted with —O—, 2-(4-phenoxyphenyl)ethyl,2-(4-phenoxyphenyl)propyl, 2-(2-phenoxyphenyl)propyl,4-biphenylylmethyl, 3-biphenylylethyl, 4-biphenylylethyl,4-biphenylylpropyl, 2-(2-biphenylyl)propyl and 2-(4-biphenylyl)propyl.

The examples of the phenylalkyl in which at least two hydrogens on abenzene ring are substituted with different groups are3-(2,5-dimethoxy-(3,4,6-trimethylphenyl)propyl,3-chloro-2-methylphenylmethyl, 4-chloro-2-methylphenylmethyl,5-chloro-2-methylphenylmethyl, 6-chloro-2-methylphenylmethyl,2-chloro-4-methylphenylmethyl, 3-chloro-4-methylphenylmethyl,2,3-dichloro-4-methyl-phenylmethyl, 2,5-dichloro-4-methylphenylmethyl,3,5-dichloro-4-methylphenylmethyl, 2,3,5-trichloro-4-methylphenylmethyl,2,3,5,6-tetrachloro-4-methylphenylmethyl,(2,3,4,6-tetrachloro-5-methylphenyl)methyl,2,3,4,5-tetrachloro-6-methylphenylmethyl,4-chloro-3,5-dimethylphenylmethyl, 2-chloro-3,5-dimethylphenylmethyl,2,4-dichloro-3,5-dimethylphenylmethyl,2,6-dichloro-3,5-dimethylphenylmethyl,2,4,6-trichloro-3,5-dimethylphenylmethyl, 3-bromo-2-methylphenylmethyl,4-bromo-2-methylphenylmethyl, 5-bromo-2-methylphenyl-methyl,6-bromo-2-methylphenylmethyl, 3-bromo-4-methylphenylmethyl,2,3-dibromo-4-methylphenylmethyl, 2,3,5-tribromo-4-methylphenylmethyl,2,3,5,6-tetrabromo-4-methylphenylmethyl and11-(3-chloro-4-methoxyphenyl)undecyl.

The most preferred examples of phenyl constituting the phenylalkyl arenon-substituted phenyl and phenyl having at least one of fluorine, alkylhaving a carbon atom number of 1 to 4, vinyl and methoxy as asubstituent.

The examples of the phenylalkyl in which —CH₂— in alkylene issubstituted with —O— or —CH═CH— are 3-phenoxypropyl, 1-phenylvinyl,2-phenylvinyl, 3-phenyl-2-propenyl, 4-phenyl-4-pentenyl and13-phenyl-12-tridecenyl.

The examples of the phenylalkenyl in which hydrogen on a benzene ring issubstituted with fluorine or methyl are 4-fluorophenylvinyl,2,3-difluorophenylvinyl, 2,3,4,5,6-pentafluorophenylvinyl and4-methylphenylvinyl.

The most preferred examples of R¹ are alkyl having a carbon atom numberof 2 to 8 (ethyl, isobutyl, isooctyl and the like), phenyl, halogenatedphenyl, phenyl having at least one methyl, methoxyphenyl, naphthyl,phenylmethyl, phenylethyl, phenylbutyl, 2-phenylpropyl,1-methyl-2-phenylethyl, pentafluorophenylpropyl, 4-ethylphenylethyl,3-ethylphenylethyl, 4-(1,1-dimethylethyl)phenylethyl,4-vinylphenylethyl, 1-(4-vinylphenyl)ethyl, 4-methoxyphenylpropyl andphenoxypropyl.

A² in Formula (1) is a group having an α-haloester group.

The group having an α-haloester group means a group havingα-halocarbonyloxy as an end group. An atom transfer radicalpolymerization method is known as a polymerization method using thisα-halocarbonyloxy group as an initiating group for radicalpolymerization. A polymerization catalyst used in this method is a metalcomplex comprising the eighth, ninth, tenth or eleventh element in theperiodic table as a central metal atom. It is known that the grouphaving α-halocarbonyloxy has an excellent polymerization initiatingability in this atom transfer radical polymerization. It is well knownas well that this polymerization is living fation.

That is, the compound (1) has an excellent polymerization initiatingability under the presence of a transition metal complex and cancontinue to maintain a living polymerization.

The compound (1) can initiate polymerization of all radicallypolymerizable monomers, and it can allow particularly styrene basederivatives to exhibit an excellent living polymerization.

The silicon compound of the present invention has α-halocarbonyloxy asan end group and therefore can be derived into a lot of derivatives byapplying various organic reactions. For example, the compound (1) can bederived into silsesquioxanes having an organic metal functional group byreacting it with lithium, magnesium or zinc. To be specific, thecompound (1) is reacted with zinc and derived into silsesquioxane havingan organic zinc functional group, and then aldehyde and ketone are addedthereto, whereby it can be converted into alcohols. That is,silsesquioxane having an organic zinc functional group is useful as anintermediate raw material used for a so-called Reformatsky reaction.

An α-halocarbonyloxy group in the compound (1) has a strongelectrophilicity, and therefore it can be converted into an amino groupand a mercapto group using various nucleophilic reagents. Further, thecompound (1) is treated with enamine to be converted into an imine salt,and this imine salt is hydrolyzed, whereby it can be converted intoketone. That is, the compound (1) is also useful as an intermediate rawmaterial used for a stork-enamine reaction. Silsesquioxane derivativeshaving various organic functional groups and polymerizable functionalgroups can be prepared as well by reacting the compound (1) withaliphatic or aromatic Grignard reagents. Accordingly, the siliconcompound of the present invention can be used not only as apolymerization initiator but also as an intermediate useful for variousorganic syntheses.

The preferred example of A¹ is a group represented by Formula (2):

in Formula (2), X¹ is halogen; R² is alkyl having a carbon atom numberof 1 to 20, aryl having a carbon atom number of 6 to 20 or aralkylhaving a carbon atom number of 7 to 20; R³ is hydrogen, alkyl having acarbon atom number of 1 to 20, aryl having a carbon atom number of 6 to20 or aralkyl having a carbon atom number of 7 to 20; Z¹ is alkylenehaving a carbon atom number of 1 to 20 or alkenylene having a carbonatom number of 3 to 8; and in these alkylene and alkenylene, optional—CH₂— may be substituted with —O—. The preferred example of Z¹ is—C₂H₄—O—C₃H₆—, —C₃H₆— or —C₂H₄—. The examples of halogen are chlorine,bromine and iodine. Chlorine and bromine are most preferred as aninitiating group for atom transfer radical polymerization.

Next, a production process for the silicon compound of the presentinvention shall be explained. The preferred raw material is a siliconcompound represented by Formula (3):

In Formula (3), R¹ has the same meaning as that of R¹ in Formula (1),and A² is an organic group having a hydroxyl group at an end.

This compound (3) used as a raw material is reacted with acid halide inwhich halogen is bonded to carbon in an α-position, whereby it can bederived into the compound (1). Then, the more preferred raw material inthe present invention is a silicon compound represented by Formula (4):

All R¹²'s in Formula (4) are the same group selected from alkyl having acarbon atom number of 1 to 8 in which optional hydrogens may besubstituted with fluorine and in which optional —CH₂— may be substitutedwith —O—, —CH═CH—, cycloalkylene or cycloalkenylene, phenyl in whichoptional hydrogens may be substituted with halogen, methyl or methoxy,non-substituted naphthyl and phenylalkyl constituted from phenyl inwhich optional hydrogens may be substituted with fluorine, alkyl havinga carbon atom number of 1 to 4, vinyl or methoxy and alkylene which hasa carbon atom number of 1 to 8 and in which optional —CH₂— may besubstituted with —O—.

Z¹ in Formula (4) is alkylene having a carbon atom number of 1 to 20 oralkenylene having a carbon atom number of 3 to 8. In these alkylene andalkenylene, optional —CH₂— may be substituted with —O—.

A synthetic route shown in the following scheme 1 and scheme 2 is one ofthe specific examples of a process for producing the compound (4). Thatis, a compound (A-1) is reacted with acetoxyethyltrichlorosilane at aroom temperature under the presence of triethylamine usingtetrahydrofuran as a solvent to prepare a compound B. Then, the compoundB is subjected to transesterification reaction in methanol under thepresence of a sulfuric acid catalyst, whereby a compound C havinghydroxyalkyl can be prepared. The compound (A-1) in the scheme 1 isobtained by obtaining polysilsesquioxane by hydrolyzing a siliconcompound having three hydrolyzable groups and then reacting it withmonovalent alkali metal hydroxide in tetrahydrofuran. The compound (A-1)is obtained as well by hydrolyzing a silicon compound having threehydrolyzable groups under the presence of alkali metal hydroxide in anoxygen-containing organic solvent and subjecting it to polycondensation.A compound (A-2) may be used in place of the compound (A-1). Thecompound (A-2) is described in Organometallics, 10, 2526-(1991). In thefollowing scheme, Ph is phenyl; THF is tetrahydrofuran; and TEA istriethylamine.

The compound (4) can be produced by a process of Feher et al. Theprocess of Feher et al is described in Chemical Communications(Cambridge, United Kingdom), 1289 to 1290 (1990). The compound (4) canbe produced by making use of the process of Feher et al for a part ofthe synthetic route.

One of the specific examples thereof shall be shown in a scheme 3 to ascheme 5.

That is, the compound (A-1) is reacted with vinyltrichlorosilane at aroom temperature under the presence of triethylamine usingtetrahydrofuran as a solvent to prepare a compound (D). Then, oneequivalent of trifluoromethanesulfonic acid is added to a vinyl group ofthe compound (D) to prepare a compound (E). The compound (E) thusobtained is hydrolyzed, whereby a compound (C) can be obtained. Also, inthe case of this route, the compound (A-2) can be used in place of thecompound (A-1).

A compound (6) which is a preferred example of the compound of thepresent invention can be obtained by reacting the compound (4) thusobtained with a compound (5):

In Formula (5), X² is halogen, and the examples thereof are chlorine,bromine and iodine. X¹, R² and R³ each have the same meanings as thoseof these codes in Formula (2). X¹ and X² may be the same or different.

R¹² and Z¹ in Formula (6) each have the same meanings as those of thesecodes in Formula (4), and R², R³ and X¹ each have the same meanings asthose of these codes in Formula (2).

The compound (4) is readily reacted with the compound (5) to become anester. Hydrogen halides by-produced in the reaction induces sidereactions such as dehydration, addition to a double bond site and thelike, and therefore the reaction is carried out in the coexistence oforganic bases in order to remove the hydrogen halides. The examples ofthe organic bases are pyridine, dimethylaniline, triethylamine andtetramethylurea. The other organic bases may be used as long as they caninhibit the side reactions and allow the reaction to quickly proceed.The most preferred example of the organic bases is triethylamine. Thisreaction is a nucleophilic displacement reaction which quantitativelyproceeds, and a use amount of the compound (5) is preferably 1 to 10times in terms of an equivalent ratio based on the compound (4). Anincrease in a use amount of the compound (5) makes it possible to reactthe whole compound (4) and makes it possible to shorten the reactiontime.

This reaction is usually carried out in an atmosphere of inert gas suchas argon gas and nitrogen gas using a dry organic solvent which isinactive to the raw material. The examples of the organic solvent arecyclic ethers such as tetrahydrofuran and dioxane, aromatic hydrocarbonssuch as toluene and xylene, halogenated hydrocarbons such as methylenechloride and chloroform and carbon tetrachloride. The preferred exampleof the organic solvent is methylene chloride. The reaction temperatureshall not specifically be restricted. However, the above reactionquickly goes on while generating heat, and therefore usually it iscarried out preferably under a low temperature condition. The preferredreaction temperature is 100° C. or lower, and the most referred reactiontemperature is 35° C. or lower. As a matter of fact, the reaction may becarried out while irregularly controlling the reaction temperature. Forexample, employed is a method in which the reaction is carried out whilecooling the reaction system using a dry ice-methanol bath or an ice bathin an initial stage and in which the temperature is then elevated to thevicinity of a room temperature to continue the reaction. The reactiontime shall not specifically be restricted, and usually the intendedsilicon compound can be obtained in 1 to 10 hours.

In the following explanations, the unreacted raw material compounds andthe solvents shall be referred to as “impurities”. If a distillationmethod is applied in order to remove the impurities, the liquid ismaintained under a high temperature condition for long time, andtherefore the intended compound is likely to be decomposed. Accordingly,it is preferably refined by reprecipitation operation in order toefficiently remove the impurities without damaging a purity of thecompound (6). This refining method is carried out in the followingmanner. First, the reaction liquid is dissolved in a solvent dissolvingboth of the compound (6) and the impurities. In this case, a preferredconcentration of the compound (6) is, roughly speaking, 1 to 15% byweight.

Next, such a solvent as not dissolving the compound (6) but dissolvingthe impurities, a so-called precipitant is added to the above solutionto precipitate only the compound (6). A preferred use amount of theprecipitant is 20 to 50 times based on the weight of the solvent usedfor dissolving both of the compound (6) and the impurities. This userange is a rough standard, and as is the case with the foregoingconcentration rage of the compound (6), it may not necessarily fall inthe above range.

The preferred solvent for dissolving the compound (6) is a solventhaving a large dissolving power and a relatively low boiling point. Thepreferred precipitant is a solvent which is compatible with the solventfor dissolving the compound (6) and does not dissolve the compound (6)at all and which dissolves only the impurities and has a relatively lowboiling point. The example of the preferred precipitant is loweralcohols. The particularly preferred precipitant is methanol or ethanol.A repeating frequency of the reprecipitation operation is advisablyraised in order to further elevate the refining degree.

Next, the examples of the compound (1) shall specifically be shown byusing codes defined in Table 1. Examples shown in Table 2 to Table 9 arethe examples of a case in which R¹² is ethyl, 2-methylpropyl,2,4,4-trimethylpentyl, cyclopentyl, cyclohexyl, 3,3,3-trifluoropropyl orphenyl in Formula (6) and in which Z¹ is —(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—,—(CH₂)₅— or —C₂H₄—O—C₃H₆—. The compound (1) shall not be restricted bythese examples.

T8 in the following tables means an octavalent group having a PSQskeleton shown below:

TABLE 1 Code Chemical formula Me —CH₃ Et —C₂H₅ IBu —CH₂CH(CH₃)₂ IOc—CH₂CH(CH₃)CH₂C(CH₃)₃ CPe

CHe

Ph

TFPr —CH₂CH₂CF₃ C2 —C₂H₄— C3 —C₃H₆— C4 —C₄H₈— C5 —C₅H₁₀— C2OC3—C₂H₄—O—C₃H₆— CL —Cl BR —Br

TABLE 2 No. R¹² Z¹ R² R³ X¹ Formula (6) 1 Et C2 Me H CL (Et-)₇ T8(—C2—OCO—CHMe—CL) 2 IBu C2 Me H CL (IBu-)₇ T8 (—C2—OCO—CHMe—CL) 3 IOc C2Me H CL (IOc-)₇ T8 (—C2—OCO—CHMe—CL) 4 CPe C2 Me H CL (CPe-)₇ T8(—C2—OCO—CHMe—CL) 5 CHe C2 Me H CL (CHe—)₇ T8 (—C2—OCO—CHMe—CL) 6 Ph C2Me H CL (Ph-)₇ T8 (—C2—OCO—CHMe—CL) 7 TFPr C2 Me H CL (TFPr-)₇ T8(—C2—OCO—CHMe—CL) 8 Et C3 Me H CL (Et-)₇ T8 (—C3—OCO—CHMe—CL) 9 IBu C3Me H CL (IBu-)₇ T8 (—C3—OCO—CHMe—CL) 10 IOc C3 Me H CL (IOc-)₇T8(—C3—OCO—CHMe—CL) 11 CPe C3 Me H CL (CPe-)₇ T8 (—C3—OCO—CHMe—CL) 12CHe C3 Me H CL (CHe—)₇ T8 (—C3—OCO—CHMe—CL) 13 Ph C3 Me H CL (Ph-)₇ T8(—C3—OCO—CHMe—CL) 14 TFPr C3 Me H CL (TFPr-)₇ T8 (—C3—OCO—CHMe—CL) 15 EtC4 Me H CL (Et-)₇ T8 (—C4—OCO—CHMe—CL) 16 IBu C4 Me H CL (IBu-)₇ T8(—C4—OCO—CHMe—CL) 17 IOc C4 Me H CL (IOc-)₇ T8 (—C4—OCO—CHMe—CL) 18 CPeC4 Me H CL (CPe-)₇ T8 (—C4—OCO—CHMe—CL) 19 CHe C4 Me H CL (CHe—)₇ T8(—C4—OCO—CHMe—CL) 20 Ph C4 Me H CL (Ph-)₇ T8 (—C4—OCO—CHMe—CL) 21 TFPrC4 Me H CL (TFPr-)₇ T8 (—C4—OCO—CHMe—CL) 22 Et C5 Me H CL (Et-)₇ T8(—C5—OCO—CHMe—CL) 23 IBu C5 Me H CL (IBu-)₇ T8 (—C5—OCO—CHMe—CL) 24 IOcC5 Me H CL (IOc-)₇ T8 (—C5—OCO—CHMe—CL) 25 CPe C5 Me H CL (CPe-)₇ T8(—C5—OCO—CHMe—CL) 26 CHe C5 Me H CL (CHe—)₇ T8 (—C5—OCO—CHMe—CL) 27 PhC5 Me H CL (Ph-)₇ T8 (—C5—OCO—CHMe—CL) 28 TFPr C5 Me H CL (TFPr-)₇ T8(—C5—OCO—CHMe—CL) 29 Et C2OC3 Me H CL (Et-)₇ T8 (—C2OC3—OCO—CHMe—CL) 30IBu C2OC3 Me H CL (IBu-)₇ T8 (—C2OC3—OCO—CHMe—CL)

TABLE 3 No. R¹² Z¹ R² R³ X¹ Formula (6) 31 IOc C2OC3 Me H CL (IOc-)₇ T8(—C2OC3—OCO—CHMe—CL) 32 CPe C2OC3 Me H CL (CPe-)₇ T8(—C2OC3—OCO—CHMe—CL) 33 CHe C2OC3 Me H CL (CHe—)₇ T8(—C2OC3—OCO—CHMe—CL) 34 Ph C2OC3 Me H CL (Ph-)₇ T8 (—C2OC3—OCO—CHMe—CL)35 TFPr C2OC3 Me H CL (TFPr-)₇ T8 (—C2OC3—OCO—CHMe—CL) 36 Et C2 Me Me CL(Et-)₇ T8 (—C2—OCO—CMe₂—CL) 37 IBu C2 Me Me CL (IBu-)₇ T8(—C2—OCO—CMe₂—CL) 38 IOc C2 Me Me CL (IOc-)₇ T8 (—C2—OCO—CMe₂—CL) 39 CPeC2 Me Me CL (CPe-)₇ T8 (—C2—OCO—CMe₂—CL) 40 CHe C2 Me Me CL (CHe—)₇ T8(—C2—OCO—CMe₂—CL) 41 Ph C2 Me Me CL (Ph-)₇ T8 (—C2—OCO—CMe₂—CL) 42 TFPrC2 Me Me CL (TFPr-)₇ T8 (—C2—OCO—CMe₂—CL) 43 Et C3 Me Me CL (Et-)₇ T8(—C3—OCO—CMe₂—CL) 44 IBu C3 Me Me CL (IBu-)₇ T8 (—C3—OCO—CMe₂—CL) 45 IOcC3 Me Me CL (IOc-)₇ T8 (—C3—OCO—CMe₂—CL) 46 CPe C3 Me Me CL (CPe-)₇ T8(—C3—OCO—CMe₂—CL) 47 CHe C3 Me Me CL (CHe—)₇ T8 (—C3—OCO—CMe₂—CL) 48 PhC3 Me Me CL (Ph-)₇ T8 (—C3—OCO—CMe₂—CL) 49 TFPr C3 Me Me CL (TFPr-)₇ T8(—C3—OCO—CMe₂—CL) 50 Et C4 Me Me CL (Et-)₇ T8 (—C4—OCO—CMe₂—CL) 51 IBuC4 Me Me CL (IBu-)₇ T8 (—C4—OCO—CMe₂—CL) 52 IOc C4 Me Me CL (IOc-)₇ T8(—C4—OCO—CMe₂—CL) 53 CPe C4 Me Me CL (CPe-)₇ T8 (—C4—OCO—CMe₂—CL) 54 CHeC4 Me Me CL (CHe—)₇ T8 (—C4—OCO—CMe₂—CL) 55 Ph C4 Me Me CL (Ph-)₇ T8(—C4—OCO—CMe₂—CL) 56 TFPr C4 Me Me CL (TFPr-)₇ T8 (—C4—OCO—CMe₂—CL) 57Et C5 Me Me CL (Et-)₇ T8 (—C5—OCO—CMe₂—CL) 58 IBu C5 Me Me CL (IBu-)₇ T8(—C5—OCO—CMe₂—CL) 59 IOc C5 Me Me CL (IOc-)₇ T8 (—C5—OCO—CMe₂—CL) 60 CPeC5 Me Me CL (CPe-)₇ T8 (—C5—OCO—CMe₂—CL)

TABLE 4 No. R¹² Z¹ R² R³ X¹ Formula (6) 61 CHe C5 Me Me CL (CHe—)₇ T8(—C5—OCO—CMe₂—CL) 62 Ph C5 Me Me CL (Ph-)₇ T8 (—C5—OCO—CMe₂—CL) 63 TFPrC5 Me Me CL (TFPr-)₇ T8 (—C5—OCO—CMe₂—CL) 64 Et C2OC3 Me Me CL (Et-)₇ T8(—C2OC3—OCO—CMe₂—CL) 65 IBu C2OC3 Me Me CL (IBu-)₇ T8(—C2OC3—OCO—CMe₂—CL) 66 IOc C2OC3 Me Me CL (IOc-)₇ T8(—C2OC3—OCO—CMe₂—CL) 67 CPe C2OC3 Me Me CL (CPe-)₇ T8(—C2OC3—OCO—CMe₂—CL) 68 CHe C2OC3 Me Me CL (CHe—)₇ T8(—C2OC3—OCO—CMe₂—CL) 69 Ph C2OC3 Me Me CL (Ph-)₇ T8 (—C2OC3—OCO—CMe₂—CL)70 TFPr C2OC3 Me Me CL (TFPr-)₇ T8 (—C2OC3—OCO—CMe₂—CL) 71 Et C2 Et EtCL (Et-)₇ T8 (—C2—OCO—CEt₂—CL) 72 IBu C2 Et Et CL (IBu-)₇ T8(—C2—OCO—CEt₂—CL) 73 IOc C2 Et Et CL (IOc-)₇ T8 (—C2—OCO—CEt₂—CL) 74 CPeC2 Et Et CL (CPe-)₇ T8 (—C2—OCO—CEt₂—CL) 75 CHe C2 Et Et CL (CHe—)₇ T8(—C2—OCO—CEt₂—CL) 76 Ph C2 Et Et CL (Ph-)₇ T8 (—C2—OCO—CEt₂—CL) 77 TFPrC2 Et Et CL (TFPr-)₇ T8 (—C2—OCO—CEt₂—CL) 78 Et C3 Et Et CL (Et-)₇ T8(—C3—OCO—CEt₂—CL) 79 IBu C3 Et Et CL (IBu-)₇ T8 (—C3—OCO—CEt₂—CL) 80 IOcC3 Et Et CL (IOc-)₇ T8 (—C3—OCO—CEt₂—CL) 81 CPe C3 Et Et CL (CPe-)₇ T8(—C3—OCO—CEt₂—CL) 82 CHe C3 Et Et CL (CHe—)₇ T8 (—C3—OCO—CEt₂—CL) 83 PhC3 Et Et CL (Ph-)₇ T8 (—C3—OCO—CEt₂—CL) 84 TFPr C3 Et Et CL (TFPr-)₇ T8(—C3—OCO—CEt₂—CL) 85 Et C4 Et Et CL (Et-)₇ T8 (—C4—OCO—CEt₂—CL) 86 IBuC4 Et Et CL (IBu-)₇ T8 (—C4—OCO—CEt₂—CL) 87 IOc C4 Et Et CL (IOc-)₇ T8(—C4—OCO—CEt₂—CL) 88 CPe C4 Et Et CL (CPe-)₇ T8 (—C4—OCO—CEt₂—CL) 89 CHeC4 Et Et CL (CHe—)₇ T8 (—C4—OCO—CEt₂—CL) 90 Ph C4 Et Et CL (Ph-)₇ T8(—C4—OCO—CEt₂—CL)

TABLE 5 No. R¹² Z¹ R² R³ X¹ Formula (6) 91 TFPr C4 Et Et CL (TFPr-)₇ T8(—C4—OCO—CEt₂—CL) 92 Et C5 Et Et CL (Et-)₇ T8 (—C5—OCO—CEt₂—CL) 93 IBuC5 Et Et CL (IBu-)₇ T8 (—C5—OCO—CEt₂—CL) 94 IOc C5 Et Et CL (IOc-)₇ T8(—C5—OCO—CEt₂—CL) 95 CPe C5 Et Et CL (CPe-)₇ T8 (—C5—OCO—CEt₂—CL) 96 CHeC5 Et Et CL (CHe—)₇ T8 (—C5—OCO—CEt₂—CL) 97 Ph C5 Et Et CL (Ph-)₇ T8(—C5—OCO—CEt₂—CL) 98 TFPr C5 Et Et CL (TFPr-)₇ T8 (—C5—OCO—CEt₂—CL) 99Et C2OC3 Et Et CL (Et-)₇ T8 (—C2OC3—OCO—CEt₂—CL) 100 IBu C2OC3 Et Et CL(IBu-)₇ T8 (—C2OC3—OCO—CEt₂—CL) 101 IOc C2OC3 Et Et CL (IOc-)₇ T8(—C2OC3—OCO—CEt₂—CL) 102 CPe C2OC3 Et Et CL (CPe-)₇ T8(—C2OC3—OCO—CEt₂—CL) 103 CHe C2OC3 Et Et CL (CHe—)₇ T8(—C2OC3—OCO—CEt₂—CL) 104 Ph C2OC3 Et Et CL (Ph-)₇ T8(—C2OC3—OCO—CEt₂—CL) 105 TFPr C2OC3 Et Et CL (TFPr-)₇ T8(—C2OC3—OCO—CEt₂—CL) 106 Et C2 Me H BR (Et-)₇ T8 (—C2—OCO—CHMe—BR) 107IBu C2 Me H BR (IBu-)₇ T8 (—C2—OCO—CHMe—BR) 108 IOc C2 Me H BR (IOc-)₇T8 (—C2—OCO—CHMe—BR) 109 CPe C2 Me H BR (CPe-)₇ T8 (—C2—OCO—CHMe—BR) 110CHe C2 Me H BR (CHe—)₇ T8 (—C2—OCO—CHMe—BR) 111 Ph C2 Me H BR (Ph-)₇ T8(—C2—OCO—CHMe—BR) 112 TFPr C2 Me H BR (TFPr -)₇ T8 (—C2—OCO—CHMe—BR) 113Et C3 Me H BR (Et-)₇ T8 (—C3—OCO—CHMe—BR) 114 IBu C3 Me H BR (IBu-)₇ T8(—C3—OCO—CHMe—BR) 115 IOc C3 Me H BR (IOc-)₇ T8(—C3—OCO—CHMe—BR) 116 CPeC3 Me H BR (CPe-)₇ T8 (—C3—OCO—CHMe—BR) 117 CHe C3 Me H BR (CHe—)₇ T8(—C3—OCO—CHMe—BR) 118 Ph C3 Me H BR (Ph-)₇ T8 (—C3—OCO—CHMe—BR) 119 TFPrC3 Me H BR (TFPr-)₇ T8 (—C3—OCO—CHMe—BR) 120 Et C4 Me H BR (Et-)₇ T8(—C4—OCO—CHMe—BR)

TABLE 6 No. R¹² Z¹ R² R³ X¹ Formula (6) 121 IBu C4 Me H BR (IBu-)₇ T8(—C4—OCO—CHMe—BR) 122 IOc C4 Me H BR (IOc-)₇ T8 (—C4—OCO—CHMe—BR) 123CPe C4 Me H BR (CPe-)₇ T8 (—C4—OCO—CHMe—BR) 124 CHe C4 Me H BR (CHe—)₇T8 (—C4—OCO—CHMe—BR) 125 Ph C4 Me H BR (Ph-)₇ T8 (—C4—OCO—CHMe—BR) 126TFPr C4 Me H BR (TFPr-)₇ T8 (—C4—OCO—CHMe—BR) 127 Et C5 Me H BR (Et-)₇T8 (—C5—OCO—CHMe—BR) 128 IBu C5 Me H BR (IBu-)₇ T8 (—C5—OCO—CHMe—BR) 129IOc C5 Me H BR (IOc-)₇ T8 (—C5—OCO—CHMe—BR) 130 CPe C5 Me H BR (CPe-)₇T8 (—C5—OCO—CHMe—BR) 131 CHe C5 Me H BR (CHe—)₇ T8 (—C5—OCO—CHMe—BR) 132Ph C5 Me H BR (Ph-)₇ T8 (—C5—OCO—CHMe—BR) 133 TFPr C5 Me H BR (TFPr-)₇T8 (—C5—OCO—CHMe—BR) 134 Et C2OC3 Me H BR (Et-)₇ T8 (—C2OC3—OCO—CHMe—BR)135 IBu C2OC3 Me H BR (IBu-)₇ T8 (—C2OC3—OCO—CHMe—BR) 136 IOc C2OC3 Me HBR (IOc-)₇ T8 (—C2OC3—OCO—CHMe—BR) 137 CPe C2OC3 Me H BR (CPe-)₇ T8(—C2OC3—OCO—CHMe—BR) 138 CHe C2OC3 Me H BR (CHe—)₇ T8(—C2OC3—OCO—CHMe—BR) 139 Ph C2OC3 Me H BR (Ph-)₇ T8 (—C2OC3—OCO—CHMe—BR)140 TFPr C2OC3 Me H BR (TFPr-)₇ T8 (—C2OC3—OCO—CHMe—BR) 141 Et C2 Me MeBR (Et-)₇ T8 (—C2—OCO—CMe₂—BR) 142 IBu C2 Me Me BR (IBu-)₇ T8(—C2—OCO—CMe₂—BR) 143 IOc C2 Me Me BR (IOc-)₇ T8 (—C2—OCO—CMe₂—BR) 144CPe C2 Me Me BR (CPe-)₇ T8 (—C2—OCO—CMe₂—BR) 145 CHe C2 Me Me BR (CHe—)₇T8 (—C2—OCO—CMe₂—BR) 146 Ph C2 Me Me BR (Ph-)₇ T8 (—C2—OCO—CMe₂—BR) 147TFPr C2 Me Me BR (TFPr-)₇ T8 (—C2—OCO—CMe₂—BR) 148 Et C3 Me Me BR (Et-)₇T8 (—C3—OCO—CMe₂—BR) 149 IBu C3 Me Me BR (IBu-)₇ T8 (—C3—OCO—CMe₂—BR)150 IOc C3 Me Me BR (IOc-)₇ T8 (—C3—OCO—CMe₂—BR)

TABLE 7 No. R¹² Z¹ R² R³ X¹ Formula (6) 151 CPe C3 Me Me BR (CPe-)₇ T8(—C3—OCO—CMe₂—BR) 152 CHe C3 Me Me BR (CHe—)₇ T8 (—C3—OCO—CMe₂—BR) 153Ph C3 Me Me BR (Ph-)₇ T8 (—C3—OCO—CMe₂—BR) 154 TFPr C3 Me Me BR (TFPr-)₇T8 (—C3—OCO—CMe₂—BR) 155 Et C4 Me Me BR (Et-)₇ T8 (—C4—OCO—CMe₂—BR) 156IBu C4 Me Me BR (IBu-)₇ T8 (—C4—OCO—CMe₂—BR) 157 IOc C4 Me Me BR (IOc-)₇T8 (—C4—OCO—CMe₂—BR) 158 CPe C4 Me Me BR (CPe-)₇ T8 (—C4—OCO—CMe₂—BR)159 CHe C4 Me Me BR (CHe—)₇ T8 (—C4—OCO—CMe₂—BR) 160 Ph C4 Me Me BR(Ph-)₇ T8 (—C4—OCO—CMe₂—BR) 161 TFPr C4 Me Me BR (TFPr-)₇ T8(—C4—OCO—CMe₂—BR) 162 Et C5 Me Me BR (Et-)₇ T8 (—C5—OCO—CMe₂—BR) 163 IBuC5 Me Me BR (IBu-)₇ T8 (—C5—OCO—CMe₂—BR) 164 IOc C5 Me Me BR (IOc-)₇ T8(—C5—OCO—CMe₂—BR) 165 CPe C5 Me Me BR (CPe-)₇ T8 (—C5—OCO—CMe₂—BR) 166CHe C5 Me Me BR (CHe—)₇ T8 (—C5—OCO—CMe₂—BR) 167 Ph C5 Me Me BR (Ph-)₇T8 (—C5—OCO—CMe₂—BR) 168 TFPr C5 Me Me BR (TFPr-)₇ T8 (—C5—OCO—CMe₂—BR)169 Et C2OC3 Me Me BR (Et-)₇ T8 (—C2OC3—OCO—CMe₂—BR) 170 IBu C2OC3 Me MeBR (IBu-)₇ T8 (—C2OC3—OCO—CMe₂—BR) 171 IOc C2OC3 Me Me BR (IOc-)₇ T8(—C2OC3—OCO—CMe₂—BR) 172 CPe C2OC3 Me Me BR (CPe-)₇ T8(—C2OC3—OCO—CMe₂—BR) 173 CHe C2OC3 Me Me BR (CHe—)₇ T8(—C2OC3—OCO—CMe₂—BR) 174 Ph C2OC3 Me Me BR (Ph-)₇ T8(—C2OC3—OCO—CMe₂—BR) 175 TFPr C2OC3 Me Me BR (TFPr-)₇ T8(—C2OC3—OCO—CMe₂—BR) 176 Et C2 Et Et BR (Et-)₇ T8 (—C2—OCO—CEt₂—BR) 177IBu C2 Et Et BR (IBu-)₇ T8 (—C2—OCO—CEt₂—BR) 178 IOc C2 Et Et BR (IOc-)₇T8 (—C2—OCO—CEt₂—BR) 179 CPe C2 Et Et BR (CPe-)₇ T8 (—C2—OCO—CEt₂—BR)180 CHe C2 Et Et BR (CHe—)₇ T8 (—C2—OCO—CEt₂—BR)

TABLE 8 No. R¹² Z¹ R² R³ X¹ Formula (6) 151 CPe C3 Me Me BR (CPe-)₇ T8(—C3—OCO—CMe₂—BR) 152 CHe C3 Me Me BR (CHe—)₇ T8 (—C3—OCO—CMe₂—BR) 153Ph C3 Me Me BR (Ph-)₇ T8 (—C3—OCO—CMe₂—BR) 154 TFPr C3 Me Me BR (TFPr-)₇T8 (—C3—OCO—CMe₂—BR) 155 Et C4 Me Me BR (Et-)₇ T8 (—C4—OCO—CMe₂—BR) 156IBu C4 Me Me BR (IBu-)₇ T8 (—C4—OCO—CMe₂—BR) 157 IOc C4 Me Me BR (IOc-)₇T8 (—C4—OCO—CMe₂—BR) 158 CPe C4 Me Me BR (CPe-)₇ T8 (—C4—OCO—CMe₂—BR)159 CHe C4 Me Me BR (CHe—)₇ T8 (—C4—OCO—CMe₂—BR) 160 Ph C4 Me Me BR(Ph-)₇ T8 (—C4—OCO—CMe₂—BR) 161 TFPr C4 Me Me BR (TFPr-)₇ T8(—C4—OCO—CMe₂—BR) 162 Et C5 Me Me BR (Et-)₇ T8 (—C5—OCO—CMe₂—BR) 163 IBuC5 Me Me BR (IBu-)₇ T8 (—C5—OCO—CMe₂—BR) 164 IOc C5 Me Me BR (IOc-)₇ T8(—C5—OCO—CMe₂—BR) 165 CPe C5 Me Me BR (CPe-)₇ T8 (—C5—OCO—CMe₂—BR) 166CHe C5 Me Me BR (CHe—)₇ T8 (—C5—OCO—CMe₂—BR) 167 Ph C5 Me Me BR (Ph-)₇T8 (—C5—OCO—CMe₂—BR) 168 TFPr C5 Me Me BR (TFPr-)₇ T8 (—C5—OCO—CMe₂—BR)169 Et C2OC3 Me Me BR (Et-)₇ T8 (—C2OC3—OCO—CMe₂—BR) 170 IBu C2OC3 Me MeBR (IBu-)₇ T8 (—C2OC3—OCO—CMe₂—BR) 171 IOc C2OC3 Me Me BR (IOc-)₇ T8(—C2OC3—OCO—CMe₂—BR) 172 CPe C2OC3 Me Me BR (CPe-)₇ T8(—C2OC3—OCO—CMe₂—BR) 173 CHe C2OC3 Me Me BR (CHe—)₇ T8(—C2OC3—OCO—CMe₂—BR) 174 Ph C2OC3 Me Me BR (Ph-)₇ T8(—C2OC3—OCO—CMe₂—BR) 175 TFPr C2OC3 Me Me BR (TFPr-)₇ T8(—C2OC3—OCO—CMe₂—BR) 176 Et C2 Et Et BR (Et-)₇ T8 (—C2—OCO—CEt₂—BR) 177IBu C2 Et Et BR (IBu-)₇ T8 (—C2—OCO—CEt₂—BR) 178 IOc C2 Et Et BR (IOc-)₇T8 (—C2—OCO—CEt₂—BR) 179 CPe C2 Et Et BR (CPe-)₇ T8 (—C2—OCO—CEt₂—BR)180 CHe C2 Et Et BR (CHe—)₇ T8 (—C2—OCO—CEt₂—BR)

TABLE 9 No. R¹² Z¹ R² R³ X¹ Formula (6) 181 Ph C2 Et Et BR (Ph-)₇ T8(—C2—OCO—CEt₂—BR) 182 TFPr C2 Et Et BR (TFPr-)₇ T8 (—C2—OCO—CEt₂—BR) 183Et C3 Et Et BR (Et-)₇ T8 (—C3—OCO—CEt₂—BR) 184 IBu C3 Et Et BR (IBu-)₇T8 (—C3—OCO—CEt₂—BR) 185 IOc C3 Et Et BR (IOc-)₇ T8 (—C3—OCO—CEt₂—BR)186 CPe C3 Et Et BR (CPe-)₇ T8 (—C3—OCO—CEt₂—BR) 187 CHe C3 Et Et BR(CHe—)₇ T8 (—C3—OCO—CEt₂—BR) 188 Ph C3 Et Et BR (Ph-)₇ T8(—C3—OCO—CEt₂—BR) 189 TFPr C3 Et Et BR (TFPr-)₇ T8 (—C3—OCO—CEt₂—BR) 190Et C4 Et Et BR (Et-)₇ T8 (—C4—OCO—CEt₂—BR) 191 IBu C4 Et Et BR (IBu-)₇T8 (—C4—OCO—CEt₂—BR) 192 IOc C4 Et Et BR (IOc-)₇ T8 (—C4—OCO—CEt₂—BR)193 CPe C4 Et Et BR (CPe-)₇ T8 (—C4—OCO—CEt₂—BR) 194 CHe C4 Et Et BR(CHe—)₇ T8 (—C4—OCO—CEt₂—BR) 195 Ph C4 Et Et BR (Ph-)₇ T8(—C4—OCO—CEt₂—BR) 196 TFPr C4 Et Et BR (TFPr-)₇ T8 (—C4—OCO—CEt₂—BR) 197Et C5 Et Et BR (Et-)₇ T8 (—C5—OCO—CEt₂—BR) 198 IBu C5 Et Et BR (IBu-)₇T8 (—C5—OCO—CEt₂—BR) 199 IOc C5 Et Et BR (IOc-)₇ T8 (—C5—OCO—CEt₂—BR)200 CPe C5 Et Et BR (CPe-)₇ T8 (—C5—OCO—CEt₂—BR) 201 CHe C5 Et Et BR(CHe—)₇ T8 (—C5—OCO—CEt₂—BR) 202 Ph C5 Et Et BR (Ph-)₇ T8(—C5—OCO—CEt₂—BR) 203 TFPr C5 Et Et BR (TFPr-)₇ T8 (—C5—OCO—CEt₂—BR) 204Et C2OC3 Et Et BR (Et-)₇ T8 (—C2OC3—OCO—CEt₂—BR) 205 IBu C2OC3 Et Et BR(IBu-)₇ T8 (—C2OC3—OCO—CEt₂—BR) 206 IOc C2OC3 Et Et BR (IOc-)₇ T8(—C2OC3—OCO—CEt₂—BR) 207 CPe C2OC3 Et Et BR (CPe-)₇ T8(—C2OC3—OCO—CEt₂—BR) 208 CHe C2OC3 Et Et BR (CHe—)₇ T8(—C2OC3—OCO—CEt₂—BR) 209 Ph C2OC3 Et Et BR (Ph-)₇ T8(—C2OC3—OCO—CEt₂—BR) 210 TFPr C2OC3 Et Et BR (TFPr-)₇ T8(—C2OC3—OCO—CEt₂—BR)

The examples shown in Table 2 to Table 9 are the preferred examples ofthe compounds of the present invention.

In addition thereto, preferred as well are the compounds in which R¹² inFormula (6) is tridecafluoro-1,1,2,2-tetrahydrooctyl and in which Z¹ is—(CH₂)₂—, —(CH₂)₃—, —(CH₂)₄—, —(CH₂)₅— or —C₂H₄—O—C₃H₆—. The compound inwhich R¹² is 3,3,3-trifluoropropyl or non-substituted phenyl in Formula(6) is most preferred.

Next, an addition-polymerizable monomer for which the compound (1) canbe used as a polymerization initiator shall be explained. Thisaddition-polymerizable monomer is a monomer having at least oneaddition-polymerizable double bond. One of the examples of amonofunctional monomer having one addition-polymerizable double bond isa (meth)acrylic acid base monomer. The specific examples thereof are(meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate,n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl(meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate,n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl(meth)acrylate, n-heptyl (meth)acrylate, n-octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate,dodecyl (meth)acrylate, phenyl (meth)acrylate, toluoyl (meth)acrylate,benzyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxypropyl(meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, stearyl (meth)acrylate,glycidyl (meth)acrylate, 3-ethyl-3-(meth)acryloyloxymethyloxetane,2-(meth)acryloyloxyethylisocyanate, 2-aminoethyl (meth)acrylate,2-(2-bromopropionylyloxy)ethyl (meth)acrylate,2-(2-bromoisobutyryloxy)ethyl (meth)acrylate,1-(meth)acryloxy-2-phenyl-2-(2,2,6,6-tetramethyl-piperidinyloxy)ethane,(1-(4-((4-(meth)acryloxy)ethoxyethyl)phenylethoxy)piperidine,γ-(methacryloyloxypropyl)trimethoxysilane,3-(3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl(meth)acrylate,3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl(meth)acrylate,3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)propyl(meth)acrylate,3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)propyl(meth)acrylate,3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptaisooctylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptacyclopentylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]propyl(meth)acrylate,3-[(3,5,7,9,11,13,15-heptaphenylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)-dimethylsilyl]propyl(meth)acrylate, ethylene oxide adducts of (meth)acrylic acid,trifluoromethylmethyl (meth)acrylate, 2-trifluoromethylethyl(meth)acrylate, 2-perfluoroethylethyl (meth)acrylate,2-perfluoroethyl-2-perfluorobutylethyl (meth)acrylate, 2-perfluoroethyl(meth)acrylate, trifluoromethyl (meth)acrylate, diperfluoromethylmethyl(meth)acrylate, 2-perfluoromethyl-2-perfluoroethylethyl (meth)acrylate,2-perfluorohexylethyl (meth)acrylate, 2-perfluorodecylethyl(meth)acrylate and 2-perfluorohexadecylethyl (meth)acrylate.

Another example of the monofunctional monomer is a styrene base monomer.The specific examples thereof are styrene, vinyltoluene,α-methylstyrene, p-chlorostyrene, p-chloromethylstyrene,m-chloromethylstyrene, o-aminostyrene, p-styrenechlorosulfonic acid,styrenesulfonic acid and salts thereof, vinylphenylmethyldithiocarbamate, 2-(2-bromopropionyloxy)styrene,2-(2-bromo-isobutyryloxy)styrene,1-(2-((4-vinylphenyl)-methoxy)-1-phenylethoxy)-2,2,6,6-tetramethyl-piperidine,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaethylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane,3-(3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaisobutylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaisooctylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-(3,5,7,9,11,13,15-heptaphenylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yl)ethylstyrene,3-((3,5,7,9,11,13,15-heptaethylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]ethylstyrene,3-((3,5,7,9,11,13,15-heptaisobutylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl)ethylstyrene,3-((3,5,7,9,11,13,15-heptaisooctylpentacyclo-[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)-dimethylsilyl)ethylstyrene,3-((3,5,7,9,11,13,15-heptacyclopentylpentacyclo[9.5.1.1^(3,9).1^(5,15).1^(7,13)]-octasiloxane-1-yloxy)dimethylsilyl)ethylstyreneand3-((3,5,7,9,11,13,15-heptaphenylpentacyclo-[[9.5.1.1^(3,9).1^(5,15).1^(7,13)]octasiloxane-1-yloxy)dimethylsilyl]ethylstyrene.

The examples of the other monofunctional monomers arefluorine-containing vinyl monomers (perfluoroethylene,perfluoropropylene, vinylidene fluoride and the like),silicon-containing vinyl base monomers (vinyltrimethoxysilane,vinyltriethoxysilane and the like), maleic anhydride, maleic acid,monoalkyl esters and dialkyl esters of maleic acid, fumaric acid,monoalkyl esters and dialkyl esters of fumaric acid, maleimide basemonomers (maleimide, methylmaleimide, ethylmaleimide, propylmaleimide,butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide,stearylmaleimide, phenylmaleimide, cyclohexylmaleimide and the like),nitrile group-containing monomers (acrylonitrile, methacrylonitrile andthe like), amide group-containing monomers (acrylamide, methacrylamideand the like), vinyl ester base monomers (vinyl acetate, vinylpropionate, vinyl pivalate, vinyl benzoate, vinyl cinnamate and thelike), olefins (ethylene, propylene and the like), conjugated diene basemonomers (butadiene, isoprene and the like), halogenated vinyls (vinylchloride and the like), halogenated vinylidenes (vinylidene chloride andthe like), halogenated allyls (allyl chloride and the like), allylalcohol, vinylpyrrolidone, vinylpyridine, N-vinylcarbazole, methyl vinylketone and vinylisocyanate. Further, given as well are macromonomerswhich have one polymerizable double bond in a molecule and in which aprincipal chain is derived from styrene, (meth)acrylic acid ester andsiloxane.

The examples of multifunctional monomers having twoaddition-polymerizable double bonds are di(meth)acrylate base monomerssuch as 1,3-butanediol di(meth)acrylate, 1,4-butanedioldi(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycoldi(meth)acrylate, diethylene glycol di(meth)acrylate, neopentyl glycoldi(meth)acrylate, triethylene glycol di(meth)acrylate, tripropyleneglycol di(meth)acrylate, hydroxypivalic acid ester neopentyl glycoldi(meth)acrylate, trimethylolpropane di(meth)acrylate,bis[(meth)acryloyloxyethoxy] bisphenol A, bis[(meth)acryloyloxyethoxy]tetrabromobisphenol A, bis[(meth)acryloxypolyethoxy] bisphenol A,1,3-bis(hydroxyethyl)-5,5-dimethylhydantoin, 3-methylpentanedioldi(meth)acrylate, di(meth)acrylates of hydroxypivalic acid esterneopentyl glycol derivatives andbis[(meth)acryloyloxypropyl]tetramethyldisiloxane and divinylbenzene.Further, given as well are macromonomers which have two polymerizabledouble bonds in a molecule and in which a principal chain is derivedfrom styrene, (meth)acrylic acid ester and siloxane.

The examples of multifunctional monomers having three or moreaddition-polymerizable double bonds are trimethylolpropanetri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate,tris(2-hydroxyethylisocyanate) tri(meth)acrylate, tris(diethyleneglycol)trimelate tri(meth)acrylate,3,7,14-tris[(((meth)acryloyloxypropyl)-dimethylsiloxy)]-1,3,5,7,9,11,14-heptaethyltricyclo-[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisobutyltricyclo[7.3.3.1^(5,11)]-heptasiloxane,3,7,14-tris[(((meth)acryloyloxy-propyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaisooctyltricyclo[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)-dimethylsiloxy)]-1,3,5,7,9,11,14-heptacyclopentyl-tricyclo[7.3.3.1^(5,11)]heptasiloxane,3,7,14-tris[(((meth)acryloyloxypropyl)dimethylsiloxy)]-1,3,5,7,9,11,14-heptaphenyltricyclo[7.3.3.1^(5,11)]-heptasiloxane,octakis(3-(meth)acryloyloxypropyl-dimethylsiloxy)octasilsesquioxane andoctakis(3-(meth)acryloyloxypropyl)octasilsesquioxane. Further, given aswell are macromonomers which have two or more polymerizable double bondsin a molecule and in which a principal chain is derived from styrene,(meth)acrylic acid ester and siloxane.

The above monomers may be used alone or a plurality thereof may becopolymerized. When copolymerized, they may be random-copolymerized orblock-copolymerized.

Next, a method for subjecting an addition-polymerizable monomer to atomtransfer radical polymerization using the compound (6) as an initiatorand a transition metal complex as a catalyst shall be explained. Theatom transfer radical polymerization method in the present invention isone of living radical polymerization methods, and it is a method forradically polymerizing addition-polymerizable monomers using an organichalide or a halogenated sulfonyl compound as an initiator. This methodis disclosed in J. Am. Chem. Soc., 1995, 117, 5614, Macromolecules,1995, 28, 7901 and Science, 1996, 272, 866.

The preferred example of a transition metal complex used as apolymerization catalyst is a metal complex in which the 7th, 8th, 9th,10th or 11th group element in the periodic table is used as centermetal. More preferred catalyst is a complex of zero-valent copper,monovalent copper, divalent ruthenium, divalent iron or divalent nickel.Among them, the complex of copper is preferred. The examples of amonovalent copper compound are cuprous chloride, cuprous bromide,cuprous iodide, cuprous cyanide, cuprous oxide and cuprous perchlorate.When using the copper compounds, 2,2′-bipyridyl or derivatives thereof,1,10-phenanthroline or derivatives thereof, polyamine(tetramethylethylenediamine, pentamethyldiethylenetriamine,hexamethyltris(2-aminoethyl)amine and the like) or polycyclic alkaloidsuch as L-(−)-sparteine is added as a ligand in order to enhance thecatalyst activity. A tristriphenylphosphine complex (RuCl₂(PPh₃)₃) ofdivalent ruthenium chloride is also suited as the catalyst. When theruthenium compound is used as the catalyst, aluminum alkoxides are addedas an activating agent.

Further, a bistriphenylphosphine complex (FeCl₂(PPh₃)₂) of divalentiron, a bistriphenylphosphine complex (NiCl₂(PPh₃)₂) of divalent nickeland a bistributylphosphine complex (NiBr₂(PBu₃)₂) of divalent nickel arealso suited as the catalyst.

A solvent may be used for the polymerization reaction. The examples ofthe solvent used are hydrocarbon base solvents (benzene, toluene and thelike), ether base solvents (diethyl ether, tetrahydrofuran, diphenylether, anisole, dimethoxybenzene and the like), halogenated hydrocarbonbase solvents (methylene chloride, chloroform, chlorobenzene and thelike), ketone base solvents (acetone, methyl ethyl ketone, methylisobutyl ketone and the like), alcohol base solvents (methanol, ethanol,propanol, isopropanol, n-butyl alcohol, tert-butyl alcohol and thelike), nitrile base solvents (acetonitrile, propionitrile, benzonitrileand the like), ester base solvents (ethyl acetate, butyl acetate and thelike), carbonate base solvents (ethylene carbonate, propylene carbonateand the like), amide base solvents (N,N-dimethylformamide,N,N-dimethylacetamide and the like), hydrochlorofluorocarbon basesolvents (HCFC-141b and HCFC-225), hydrofluorocarbon (HFCs) basesolvents (HFCs having a carbon atom number of 2 to 4, 5 and 6 or more),perfluorocarbon base solvents (perfluoropentane and perfluorohexane),alicyclic hydrofluorocarbon base solvents (fluorocyclopentane andfluorocyclobutane), oxygen-containing fluorine base solvents(fluoroether, fluoropolyether fluoroketone and fluoroalcohol) and water.They may be used alone or two or more kinds thereof may be used incombination. The polymerization can be carried out as well in anemulsion system or a system in which a supercritical fluid CO₂ is usedas a medium. The solvent which can be used shall not be restricted tothese examples.

The atom transfer radical polymerization can be carried out underreduced pressure, atmospheric pressure or applied pressure according tothe kind of the addition-polymerizable monomer and the kind of thesolvent. An organic metal complex used in combination or a radicalproduced is likely to be deactivated when brought into contact withoxygen. In such case, the polymerizing speed is reduced, and a goodliving polymer is not obtained. Accordingly, it is important to carryout the polymerization under inert gas atmosphere of nitrogen or argon.In this reaction, dissolved oxygen in the polymerization system has tobe removed in advance under reduced pressure. It is possible to shiftthe reaction system to a polymerization step as it is under reducedpressure after finishing the step of removing dissolved oxygen.Conventional processes can be adopted for the atom transfer radicalpolymerization, and it shall not specifically be restricted by apolymerization process. For example, bulk polymerization, solutionpolymerization, suspension polymerization, emulsion polymerization orbulk-suspension polymerization can be adopted. The polymerizationtemperature falls in a range of 0 to 200° C., and the preferredpolymerization temperature falls in a range of a room temperature to150° C.

A polymer obtained by using the compound (6) as an initiator by theprocess described above can be represented by Formula (7). The polymerrepresented by Formula (7) shall be described as the polymer (7).

P¹ in Formula (7) is a chain of a structural unit obtained bypolymerizing an addition-polymerizable monomer, and the other codes eachhave the same meanings as those of these codes in Formula (6).

Suitable selection of the kind of the addition-polymerizable monomerused makes it possible to control the structure of the compound (7)produced. For example, if the monomer is homopolymerized, silsesquioxaneto which a homopolymer is bonded is obtained. If the plural monomers areadded at the same time and polymerized, silsesquioxane to which a randomcopolymer is bonded is obtained. If used is a method in which themonomers are successively added, for example, a method in which thesecond monomer is added after finishing the polymerization of the firstmonomer to complete the polymerization, silsesquioxane to which a blockcopolymer is bonded is obtained. Repeating of this staged polymerizationusing plural monomers makes it possible to obtain silsesquioxane towhich a multiblock copolymer is bonded. A cross-linked polymer having athree-dimensional network structure can be prepared by allowing amultifunctional monomer, if necessary, to coexist.

Silsesquioxanes to which highly branched type polymers are bonded can beobtained by using in combination a compound having a polymerizablefunctional group as well as a function as an initiator, for example,2-(2-bromopropionyloxy)ethyl (meth)acrylate,2-(2-bromoisobutyryloxy)ethyl (meth)acrylate,2-(2-bromopropionyloxy)styrene and 2-(2-bromoisobutyryloxy)styrene whenpolymerizing a usual addition-polymerizable monomer. Further, combineduse of compounds which are trialkoxysilane, polydimethylsiloxane andsilsesquioxane and which have polymerizable functional groups such as a(meth)acryl group and a styryl group makes it possible to introduce astructural unit containing a silicon atom into the structure of thepolymer. After copolymerized with an addition-polymerizable monomerhaving an initiating group which does not take part in atom transferradical polymerization, for example,1-(2-(4-vinylphenylmethoxy)-1-phenylethoxy)-2,2,6,6-tetramethylpyridine,1-(meth)acryloxy-2-phenyl-2-(2,2,6,6-tetramethyl-1-piperidinyloxy)ethane,1-(4-(4-(meth)acryloyloxyethoxyethyl)phenylethoxy)piperidine andvinylphenylmethyl dithiocarbamate, an addition-polymerizable monomer isfurther polymerized in the other polymerization mode (for example,nitroxyl polymerization and photo initiator-transfer agent-terminatorpolymerization) using the resulting polymer as an initiator, whereby agraft copolymer can be formed.

After copolymerized with a monomer having an oxetanyl group, forexample, 3-ethyl-3-(meth)acryloyloxymethyloxetane,diphenyl-4-thiophenoxyphenylsulfonium hexafluoroantimonate or(4-pentadecyloxyphenyl)phenyliodonium hexafluoroantimonate is added asan initiator to the resulting polymer, whereby it can be subjected tophotocationic polymerization.

Next, a refining method for the polymer (7) shall be explained. Thiscompound is isolated and refined by efficiently removing the unreactedaddition-polymerizable monomer. Various methods are available, and arefining method carried out by reprecipitation operation is preferred.

This refining method is carried out in the following manner.

First, a solvent which does not dissolve the polymer (7) but dissolvesthe unreacted monomer, a so-called precipitant is added to thepolymerization reaction liquid containing the polymer (7) and theunreacted monomer to precipitate only the polymer (7). A preferred useamount of the precipitant is 20 to 50 times based on the weight of thepolymerization reaction liquid described above.

The preferred precipitant is a solvent which is compatible with thesolvent used in polymerization and which does not dissolve the polymer(7) at all but dissolves only the unreacted monomer and has a relativelylow boiling point.

The examples of the preferred precipitant are lower alcohols andaliphatic hydrocarbons. The particularly preferred precipitant ismethanol and hexane. A repeating frequency of the reprecipitationoperation is advisably increased in order to further raise a removingefficiency of the unreacted monomer. This method makes it possible todeposit only the polymer (7) in a poor solvent, and the polymer canreadily be separated from the unreacted monomer by filtering operation.

The transition metal complex which is the polymerization catalystremains in the compound (7) isolated by the method described above, andtherefore problems such as coloring of the polymer, influence on thephysical properties and environmental safety are brought about in acertain case. Accordingly, this catalyst residue has to be removed infinishing the polymerization reaction. The catalyst residue can beremoved by adsorbing treatment using activated carbon.

The examples of adsorbents other than activated carbon are ion exchangeresins (acid, basic or chelate form) and inorganic adsorbents. Theinorganic adsorbents have a character of a solid acid, a solid base orneutrality. They are particles having a porous structure and thereforehave a very high adsorbing ability. It is also one of thecharacteristics of the inorganic adsorbents that they can be used in awide temperature range extending from a low temperature to a hightemperature.

The representative examples of the inorganic adsorbents are silicondioxide, magnesium oxide, silica-alumina, aluminum silicate, activatedalumina, clay base adsorbents such as acid clay and activated clay,zeolite base adsorbents, dawsonites compounds and hydrotalcitescompounds. Zeolite includes natural products and synthetic products, andeither can be used. Kinds such as a crystal form, an amorphous form, anoncrystal form, a glass form, a synthetic product and a natural productare available for silicon dioxide, and silicon dioxide of a powder formcan be used in the present invention regardless of the kind. Theexamples of natural aluminum silicate are pumice, fly ash, kaoline,bentonite, activated clay and diatomaceous earth. Synthetic aluminumsilicate has a large specific surface area and a high adsorbing ability.The hydrotalcites compound is carbonate hydrate of aluminum-magnesiumhydroxide.

The acid adsorbents and the basic adsorbents are preferably used incombination with activated carbon. The examples of the acid adsorbentsare acid clay, activated clay and aluminum silicate. The examples of thebasic adsorbents are activated alumina, the zeolite base adsorbents andthe hydrotalcites compounds each described above. These adsorbents maybe used alone or in a mixture of two or more kinds thereof. The polymer(7) produced by the atom transfer radical polymerization can be refinedby bringing into contact with activated alumina. A commercial productavailable from Aldrich Co., Ltd. can be used as activated alumina. Whenadsorbing treatment is carried out by using activated alumina incombination with the other adsorbents, the adsorbents can be mixed andbrought into contact with the compound, but they may be brought intocontact at the separate steps respectively. When brought into contactwith the adsorbent, the reaction liquid may be used as it is or may bediluted with a solvent. The diluent may be selected from usual solventsonly on the condition that it is not a poor solvent for the polymer. Atemperature for treating with the adsorbent shall not specifically berestricted. The treatment may be carried out usually at 0 to 200° C. Thepreferred temperature range is a room temperature to 180° C. A useamount of the absorbent falls in a range of 0.1 to 500% by weight basedon the weight of the polymer (7). Considering the economical efficiencyand the operability, the preferred range is 0.5 to 10% by weight.

A method of a batch system in which stirring-mixing and solid-liquidseparation are carried out by batch operation can be used forsolid-liquid contact of the absorbent and the polymer liquid. Inaddition thereto, capable of being used is a method of a continuoussystem such as a fixed layer system in which the polymer liquid isallowed to pass through a vessel charged with the adsorbent, a movinglayer system in which the liquid is allowed to pass through a movinglayer of the adsorbent and a fluidized layer system in which theadsorbent is fluidized by a liquid to carry out adsorption. Further, amixing and dispersing operation carried out by stirring can be combined,if necessary, with an operation for elevating the dispersing efficiency,such as shaking of the vessel and use of a supersonic wave. After thepolymer liquid is brought into contact with the absorbent, the absorbentis removed by a method such as filtering, centrifugal separation andsettling separation, and washing treatment is carried out if necessaryto obtain the refined polymer liquid. Treatment by the absorbent may becarried out for the polymer (7) which is the final product, and it maybe carried out for an intermediate product used for producing thispolymer. For example, in the respective polymerizing steps of the blockcopolymer obtained by the atom transfer radical polymerization, thispolymer can be isolated and subjected to adsorbing treatment. Thepolymer (7) subjected to treatment by the adsorbent may be separated bydepositing in a poor solvent or distilling off volatile components suchas the solvent under reduced pressure.

The analytical methods of a molecular weight and a molecular weightdistribution of the polymer (7) produced shall be explained. Usually, amolecular weight of an addition polymer can be measured by gelpermeation chromatography (GPC) using a calibration curve in which alinear polymer such as polystyrene and poly(methyl methacrylate) is usedas a standard sample. A molecular weight and a molecular weightdistribution of the polymer (7) can be analyzed as well by GPC.

The polymer (7) has silsesquioxane at an end part thereof, and thereforeit can readily be decomposed under an acid condition or a basiccondition. That is, an accuracy in molecular weight analysis of apolymer part can further be enhanced by cutting off an addition polymerfrom silsesquioxane and then measuring the molecular weight thereof.Hydrofluoric acid is preferably used when decomposing the polymer (7)under an acid condition. Potassium hydroxide is preferably used whendecomposing the polymer (7) under a basic condition. The polymer (7) canbe decomposed in either of a homogeneous system and a heterogeneoussystem. For example, the silsesquioxane part of the polymer (7) can bedecomposed in a homogeneous mixed system of an organic solvent(tetrahydrofuran, acetonitrile and the like) which can dissolve thepolymer (7) and hydrofluoric acid. The silsesquioxane part can bedecomposed as well in a heterogeneous mixed system of toluene andhydrofluoric acid. In this case, a phase transfer catalyst is preferablyused in combination. The examples of the phase transfer catalyst arebenzyltrimethylammonium chloride, tetramethylammonium chloride,tetrabutylammonium bromide, trioctylammonium chloride,dioctyldimethylammonium chloride, triethylamine and dimethylaniline.When using potassium hydroxide, decomposition can be carried out as wellin a mixed solvent of tetrahydrofuran, ethanol and water.

The addition polymer cut off by the above methods is measured by GPC,whereby a molecular weight of an addition polymer part in the polymer(7) can be determined. It is possible as well to determine a molecularweight of the polymer (7) by using a universal calibration curveobtained from the viscosity and the GPC data. An absolute molecularweight of the polymer (7) can be determined as well by an end groupdetermination method, a membrane osmotic pressure method, aultracentrifugal method and a light scattering method.

A preferred molecular weight of the polymer (7) falls in a range of 500to 1,000,000 for a number average molecular weight in terms ofpolystyrene. The more preferred range is 1,000 to 100,000. However, theupper limit value and the lower limit value in this range do notnecessarily have a specific meaning. The molecular weight distributionfalls preferably in a range of 1.01 to 2.0 in terms of a polydispersity(Mw/Mn).

The molecular weight of the polymer (7) can be controlled by aproportion of the addition-polymerizable monomer to the compound (6)which is an initiator. That is, a theoretical molecular weight of thegraft chain in the polymer (7) can be predicted from a mole ratio of theaddition-polymerizable monomer/the compound (6) and a consumption rateof the monomer using the following calculation equation:

Mn=(conversion rate (mole %) of monomer/100)×MW_(M)×mole ratio+MW_(I)

In the above calculation equation, Mn is a theoretical number averagemolecular weight; MW_(M) is a molecular weight of theaddition-polymerizable monomer; MW_(I) is a molecular weight of thecompound (6); and the mole ratio is a mole ratio of theaddition-polymerizable monomer to the compound (6).

When intending to obtain a polymer having the number average molecularweight range described above, a mole ratio of the addition-polymerizablemonomer to the compound (6) is controlled to about 2 to about 40,000.The preferred range of the above mole ratio is about 10 to about 5,000.The number average molecular weight can be controlled as well bychanging the polymerization time.

Any method of GPC, ¹H-NMR and gas chromatography can be adopted fordetermining a consumption rate (hereinafter referred to as “conversion”)of the monomer.

EXAMPLES

The present invention shall more specifically be explained withreference to examples, but the present invention shall not be restrictedto the following examples.

The data of molecular weights in Examples 1 to 100 arepolystyrene-standard values determined by GPC (gel permeationchromatography), and the data of molecular weights in Examples 101 to130 are poly(methyl methacrylate)-standard values determined by GPC. Themeasuring conditions of GPC are shown below.

Apparatus: JASCO GULLIVER 1500 (intelligent differential refractometerRI-1530), manufactured by JASCO Corp.Solvent: tetrahydrofuranFlow velocity: 1 ml/minuteColumn temperature: 40° C.Columns used: Examples 1 to 90: TSKguardcolumn HXL-L(GUARDCOLUMN)+TSKgel G1000H×L (exclusion limited of molecular weight(polystyrene): 1,000)+TSKgel G2000H×L (excluded critical molecularweight (polystyrene): 10,000), each manufactured by Tosoh Co., Ltd.Standard sample for calibration curve: Polymer Standards (PL),Polystyrene, manufactured by Polymer Laboratories Co., Ltd.Columns used: Examples 91 to 130: Shodex KF-G (GUARDCOLUMN)+ ShodexKF-804L (exclusion limited of molecular weight (polystyrene):400,000)×2, columns each manufactured by Showa Denko K. K.

Codes used in the examples mean the following.

Ph: phenylCh: cyclohexylCp: cyclopentylEt: ethyliBu: isobutyliOc: isooctylTFPr: trifluoropropylTDFOc: tridecafluoro-1,1,2,2-tetrahydrooctylTMS: trimethylsilylMn: number average molecular weightMw: weight average molecular weight

Example 1 Synthesis of Polyphenylsilsesquioxane Compound A

A four neck separable flask having a content volume of 2 liter equippedwith stirrer, a reflux condenser, a thermometer and a dropping funnelwas charged with ice and water (640.7 g) and toluene (200 g), and theinside of the flask was cooled to 0° C. while stirring. Next, a mixedsolution of phenyltrichlorosilane (211.5 g) and toluene (130 g) dried onmolecular sieves for a whole day and nigh was dropwise added thereto inone hour so that a temperature of the inside of the flask did not exceed2° C. Then, after stirring at a room temperature for 30 minutes, thesolution was washed with refined water, and toluene was distilled offunder reduced pressure to obtain a solid compound A (120.7 g).

The compound A had a weight average molecular weight of about 3100.

Example 2 Synthesis of Sodium-Bonded Phenylsilsesquioxane CompoundCompound B

A four neck flask of 500 ml equipped with a reflux condenser and athermometer was charged with the compound A (12.9 g) obtained above,tetrahydrofuran (250 ml) dried on molecular sieves for a whole day andnight and sodium hydroxide (4.0 g), and the flask was heated at 67° C.while stirring by means of a magnetic stirrer to maintain a refluxstate. After about 4 hours, the solution began to get cloudy bydeposition of fine powder, and refluxing was continued for one hour asit was to finish the reaction. A solid matter deposited was washed withtetrahydrofuran and separated from tetrahydrofuran by filtering, andthen it was dried under vacuum to obtain a compound B (10.1 g).

Example 3 Synthesis of Sodium-Bonded Phenylsilsesquioxane Compound(Compound B) Using Phenyltrimethoxysilane as a Raw Material

A four neck flask having a content volume of one liter equipped with areflux condenser, a thermometer and a dropping funnel was charged withphenyltrimethoxyosilane (99 g), sodium hydroxide (10 g) and 2-propanol(500 ml), and a rotator was put thereinto. Deionized water 11 g wasdropwise added thereto from the dropping funnel in about 2 minutes whilestirring at a room temperature by means of a magnetic stirrer, and thenthe flask was heated on an oil bath up to a temperature at which2-propanol was refluxed. After refluxing was started, stirring wascontinued for 1.5 hour to complete the reaction. Then, the flask waspulled up from the oil bath and left standing still a night at a roomtemperature to completely deposit a solid matter produced. The solidmatter deposited was filtrated by means of a pressure filter equippedwith a membrane filter having a pore diameter of 0.1 μm. Then, the solidmatter thus obtained was washed once with 2-propanol and dried at 70° C.for 4 hours in a vacuum dryer to obtain a compound B (66 g) of a whitesolid matter.

Example 4 Introduction of Trimethylsilyl Group into Compound B ObtainedUsing Phenyltrimethoxysilane as a Raw Material Compound C

A four neck flask having a content volume of 50 ml equipped with adropping funnel, a reflux condenser and a thermometer was charged with arotator, the compound B (1.2 g) obtained in Example 3, tetrahydrofuran(12 g) and triethylamine (1.8 g), and the flask was sealed with drynitrogen. Chlorotrimethylosilane (2.3 g) was dropwise added thereto fromthe dropping funnel at a room temperature in about one minute whilestirring by means of a magnetic stirrer. After finishing dropwiseadding, stirring was continued at a room temperature for 3 hours tocomplete the reaction. Then, 10 g of purified water was added thereto todissolve sodium chloride produced and hydrolyze unreactedchlorotrimethylsilane. The reaction mixture thus obtained wastransferred to a separating funnel and separated into an organic phaseand an aqueous phase, and the resulting organic phase was repeatedlywashed with deionized water until a washing liquid became neutral. Theorganic phase thus obtained was dried on anhydrous magnesium sulfate,filtered and concentrated under reduced pressure by means of a rotaryevaporator to obtain a compound C (1.2 g) of a white solid matter.

The compound C was subjected to structural analysis by means of ¹H-NMR,¹³C-NMR, ²⁹Si-NMR, mass spectrometry, X ray crystal structure analysisand IR analysis. It was confirmed from a ¹H-NMR chart and a ¹³C-NMRchart that a phenyl group and a trimethylsilyl group were present in anintegral ratio of 7:3. It was confirmed from ²⁹Si-NMR that three kindsof peaks of 11.547 ppm indicating a trimethylsilyl group, −77.574 ppm,−78.137 ppm and −78.424 ppm (all based on tetramethylsilane) having aphenyl group and indicating a T structure were present in a ratio of1:3:3. It was confirmed from the measuring results of a massspectrometric spectrum that the absolute molecular weight was consistentwith a theoretical molecular weight of the structure represented byFormula (8) described above. It was confirmed from the measuring resultsof crystal structure analysis by X ray crystal structure analysis thatthe compound was the structural body represented by Formula (8)described above. Confirmed from the measuring results of an IRanalytical spectrum were absorptions assigned respectively todeformation vibration of Si-Ph in 1430 and 1590 cm⁻¹, harmonic vibrationof a substituted benzene ring in 1960 to 1760 cm⁻¹, stretching vibrationof Si—O—Si in 1200 to 950 cm⁻¹ and vibration of Si—CH₃ in 1250 cm⁻¹.These results support that the compound (compound C) replaced by atrimethylsilyl group has the structure represented by Formula (8)described above, and this has made it apparent that thesodium-containing silsesquioxane compound (compound B) obtained has thestructure represented by Formula (9) described above. The T structuremeans a structure in which three oxygen atoms are bonded to an Si atom.

Example 5 Synthesis of Sodium-Bonded Cyclohexylsilsesquioxane CompoundUsing Cyclohexyltrimethoxysilane as a Raw Material

The same operation as in Example 3 is carried out, except thatcyclohexyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-bonded cyclohexylsilsesquioxane compound represented byFormula (10) can be obtained.

Example 6 Introduction of Trimethylsilyl Group into Compound (10)

The same operation as in Example 4 is carried out, except that thecompound (10) is substituted for the compound (9), whereby acyclohexylsilsesquioxane compound having a trimethylsilyl grouprepresented by Formula (11) can be obtained. Further, it can beconfirmed by subjecting the compound (11) to structural analysis by thesame operation as in Example 4 that the compound (10) described above isproduced.

Example 7 Synthesis of Sodium-Bonded Cyclopentylsilsesquioxane CompoundUsing Cyclopentyltrimethoxysilane as a Raw Material

A four neck flask having a content volume of 200 ml equipped with areflux condenser, a thermometer and a dropping funnel was charged withcyclopentyltrimethoxyosilane (19.0 g), THF (100 ml), sodium hydroxide(1.7 g) and deionized water (2.3 g), and the flask was heated whilestirring by means of a magnetic stirrer. After refluxing was started at67° C., stirring was continued for 10 hours to finish the reaction.Then, the flask was pulled up from the oil bath and left standing stilla night at a room temperature to completely deposit a solid matterproduced. The solid matter deposited was filtrated and dried undervacuum to obtain a compound of a powder-like solid matter (4.2 g).

Example 8 Introduction of Trimethylsilyl Group

A four neck flask having a content volume of 100 ml equipped with areflux condenser was charged with the compound (1.0 g) obtained inExample 7, THF (30 ml), triethylamine (0.5 g) and trimethylchlorosilane(0.7 g), and the mixture was stirred at a room temperature for 2 hourswhile stirring by means of a magnetic stirrer. After finishing thereaction, the same treatment as in confirming the structure in Example 4was carried out to obtain a compound of a powder-like solid matter (0.9g).

The compound thus obtained was analyzed by means of ¹H-NMR, ²⁹Si-NMR andX ray crystal structure analysis. It was confirmed from ¹H-NMR that acyclopentyl group and a trimethylsilyl group were present in an integralratio of 7:3. Confirmed from ²⁹Si-NMR were 8.43 ppm indicating atrimethylsilyl group and three kinds of peaks of −66.37 ppm, −67.97 ppmand −67.99 ppm having a cyclopentyl group and indicating a T structure.A ratio of the sum of the peak intensities of −67.97 ppm and −67.99 ppmto a peak intensity of −66.37 ppm was 6:1. It was confirmed from theseresults and the crystal structure obtained by the X ray crystalstructure analysis that the compound of a powder-like solid matter whichwas the object of the analysis was a silicon compound represented byFormula (12). Accordingly, it was indicated that the compound obtainedin Example 7 had a structure represented by Formula (13).

Example 9 Synthesis of Sodium-Bonded Ethylsilsesquioxane Compound UsingEthyltrimethoxysilane as Raw Material

The same operation as in Example 3 is carried out, except thatethyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-bonded ethylsilsesquioxane compound represented byFormula (14) can be obtained.

Example 10 Introduction of Trimethylsilyl Group into Compound (14)

The same operation as in Example 4 is carried out, except that thecompound (14) is substituted for the compound (9), whereby anethylsilsesquioxane compound having a trimethylsilyl group representedby Formula (15) can be obtained. Further, it can be confirmed bysubjecting the compound (15) to structural analysis by the sameoperation as in Example 4 that the compound (14) described above isproduced.

Example 11 Synthesis of Sodium-Bonded Isobutylsilsesquioxane CompoundUsing Isobutyltrimethoxysilane as a Raw Material

A four neck flask having a content volume of 200 ml equipped with areflux condenser, a thermometer and a dropping funnel was charged withisobutyltrimethoxyosilane (18.7 g), THF (100 ml), sodium hydroxide (1.8g) and deionized water (2.4 g), and the flask was heated while stirringby means of a magnetic stirrer. After refluxing was started at 67° C.,stirring was continued for 10 hours to finish the reaction. The reactionliquid was concentrated under constant pressure until a solid matter wasdeposited, and then the resulting concentrate was left standing still anight at a room temperature to completely deposit the solid matter. Thiswas filtered and dried under vacuum to obtain a compound of apowder-like solid matter (5.1 g).

Example 12 Introduction of Trimethylsilyl Group

A four neck flask having a content volume of 200 ml equipped with areflux condenser was charged with the compound of a powder-like solidmatter (1.0 g) obtained in Example 11, THF (20 ml), triethylamine (0.5g) and trimethylchlorosilane (0.8 g), and the mixture was stirred at aroom temperature for 2 hours while stirring by means of a magneticstirrer. After finishing the reaction, the same treatment as inconfirming the structure in Example 4 was carried out to obtain acompound of a powder-like solid matter (0.9 g).

The powder-like solid matter described above was subjected to structuralanalysis by means of ¹H-NMR and ²⁹Si-NMR. It was confirmed from a ¹H-NMRchart that an isobutyl group and a trimethylsilyl group were present inan integral ratio of 7:3. It was confirmed from ²⁹Si-NMR that threekinds of peaks of 8.72 ppm indicating a trimethylsilyl group, −67.38ppm, −68.01 ppm and −68.37 ppm having an isobutyl group and indicating aT structure were present in a ratio of 1:3:3. It was confirmed fromthese results that the compound of a powder-like solid matter which wasthe object of the analysis was a silicon compound represented by Formula(16). Accordingly, it was indicated that the compound obtained inExample 11 had a structure represented by Formula (17).

Example 13 Synthesis of Sodium-Bonded Isooctylsilsesquioxane CompoundUsing Isooctyltrimethoxysilane as a Raw Material

The same operation as in Example 3 is carried out, except thatisooctyltrimethoxysilane is substituted for phenyltrimethoxyosilane,whereby a sodium-bonded isooctylsilsesquioxane compound represented byFormula (18) can be obtained.

Example 14 Introduction of Trimethylsilyl Group into Compound (18)

The same operation as in Example 4 is carried out, except that thecompound (18) is substituted for the compound (9), whereby anisooctylsilsesquioxane compound having a trimethylsilyl grouprepresented by Formula (19) can be obtained. Further, it can beconfirmed by subjecting the compound (19) to structural analysis by thesame operation as in Example 4 that the compound (18) described above isproduced.

Example 15 Synthesis of Sodium-Added TrifluoropropylsilsesquioxaneCompound Using Trifluoropropyltrimethoxysilane as a Raw Material

A four neck flask having a content volume of 1 liter equipped with areflux condenser, a thermometer and a dropping funnel was charged withtrifluoropropyltrimethoxyosilane (100 g), THF (500 ml), deionized water(10.5 g) and sodium hydroxide (7.9 g), and the flask was heated on anoil bath from a room temperature up to a temperature at which THF wasrefluxed while stirring by means of a magnetic stirrer. After refluxingwas started, stirring was continued for 5 hours to complete thereaction. Thereafter, the flask was pulled up from the oil bath and leftstanding still a night at a room temperature, and then the flask was setagain on the oil bath to heat and concentrate the reaction liquid underconstant pressure until a solid matter was deposited. The productdeposited was filtrated through a pressure filter equipped with amembrane filter having a pore diameter of 0.5 μm. Then, the solid matterthus obtained was washed once with THF and dried at 80° C. for 3 hoursin a vacuum dryer to obtain 74 g of a colorless powder-like solidmatter.

Example 16 Introduction of Trimethylsilyl Group

A four neck flask having a content volume of 50 ml equipped with adropping funnel, a reflux condenser and a thermometer was charged withthe colorless powder-like solid matter (1.0 g) obtained in Example 15,THF (10 g) and triethylamine (1.0 g), and the flask was sealed with drynitrogen. Chlorotrimethylsilane (3.3 g) was dropwise added thereto at aroom temperature in about one minute while stirring by means of amagnetic stirrer. After finishing dropwise adding, stirring wascontinued at a room temperature for 3 hours to complete the reaction.Then, 10 g of purified water was added thereto to dissolve sodiumchloride produced and hydrolyze unreacted chlorotrimethylsilane. Thereaction mixture thus obtained was transferred to a separating funneland separated into an organic phase and an aqueous phase, and theresulting organic phase was repeatedly washed with deionized water untila washing liquid became neutral. The organic phase thus obtained wasdried on anhydrous magnesium sulfate, filtered and concentrated underreduced pressure by means of a rotary evaporator to obtain a compound(0.9 g) of a white solid matter.

The white power-like solid matter obtained was subjected to structuralanalysis by means of GPC, ¹H-NMR, ²⁹Si-NMR and ¹³C-NMR. It was confirmedfrom a GPC chart that the white power-like solid matter showed amonodispersibility and had a weight average molecular weight of 1570 interms of polystyrene and a purity of 98% by weight. It was confirmedfrom a ¹H-NMR chart that a trifluoropropyl group and a trimethylsilylgroup were present in an integral ratio of 7:3. It was confirmed from a29 Si-NMR chart that three peaks having a trifluoropropyl group andindicating a T structure were present in a ratio of 1:3:3 and that onepeak indicating a trimethylsilyl group was present in 12.11 ppm. It wasconfirmed from a ¹³C-NMR chart that peaks indicating a trifluoropropylgroup were present in 131 to 123 ppm, 28 to 27 ppm and 6 to 5 ppm andthat a peak indicating a trimethylsilyl group was present in 1.4 ppm. Itwas confirmed from the measuring results of a mass spectrometricspectrum that the absolute molecular weight was consistent with atheoretical molecular weight of a structural body represented by Formula(20). It was confirmed from the results of crystal structure analysis byX ray crystal structure analysis that the compound was the structuralbody represented by Formula (20). The above results show that thecolorless powder-like solid matter which is an object for the structuralanalysis has the structure represented by Formula (20). Accordingly, itis judged that the compound before trimethylsilylated has a structurerepresented by Formula (21).

Example 17 Synthesis of Acetoxyethyl-Heptaphenyloctasilsesquioxane Usingthe Compound (9) as a Raw Material

The compound (9) 10 g obtained in Example 1 and tetrahydrofuran (200 ml)were introduced into a four neck flask of 500 ml equipped with a refluxcondenser, a thermometer and a rotator. Then,acetoxyethyltrichlorosilane (3.3 g, 1.5 equivalent based on the compound(9)) was quickly added to a compound (9)/tetrahydrofuran solution, andthe solution was stirred at a room temperature for 2 hours. Then, thereaction liquid was poured into hexane (1000 g). A solid componentdeposited was recovered by suction filtration and dissolved again intoluene (90 g), and then the organic layer was washed with water (330ml). After washing was carried out three times, the organic layer wasseparated and dried on anhydrous magnesium sulfate (5 g). Thereafter,solid-liquid separation was carried out by filtration through a filter.Then, ethanol (90 g) was added to a solid component obtained byconcentrating the organic layer, and the mixture was stirred under aroom temperature condition. Further, solid-liquid separation was carriedout by means of a pressure filtering device, and a solid componentobtained was then dried (80° C., 3 hours) under reduced pressure toobtain a colorless solid matter (6.88 g, yield: 65.9%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of IR, ¹H-NMR, ¹³C-NMR and²⁹Si-NMR each shown below that the colorless solid matter obtained had astructure represented by Formula (22).

IR (KBr method: ν=1740 (C═O), 1430 (Si-Ph), 1240 (C—O), 1135 to 1090(Si-Ph), 1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, Ph-Si), 4.32 to 4.28 (t, 2H, —O—CH₂—), 1.84 (s, 3H,CH₃—(C═O)—), 1.37 to 1.33 (t, 2H, —CH₂—Si)

¹³C NMR (100 MHz, TMS standard: δ 0.0 ppm): 171.15 (C═O) 134.4 to 134.3,131.1 to 131.0, 130.2, 128.12 (Ph-Si), 60.6 (—O—CH₂—), 20.8(CH₃—(C═O)—), 13.2 (—CH₂—Si)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −67.97 (—CH₂—SiO_(1.5)),−78.36, −78.67 (Ph-SiO_(1.5))

Example 18 Synthesis of Acetoxyethyl-HeptacyclohexyloctasilsesquioxaneUsing the Compound (10) as a Raw Material

The same operation as in Example 17 is carried out, except that thecompound (10) obtained in Example 5 is substituted for the compound (9),whereby a compound represented by Formula (23) can be obtained.

Example 19 Synthesis of Acetoxyethyl-HeptacyclopentyloctasilsesquioxaneUsing the Compound (13) as a Raw Material

The same operation as in Example 17 is carried out, except that thecompound (13) obtained in Example 7 is substituted for the compound (9),whereby a compound represented by Formula (24) can be obtained.

Example 20 Synthesis of Acetoxyethyl-Heptaethyloctasilsesquioxane Usingthe Compound (14) as Raw a Material

The same operation as in Example 17 is carried out, except that thecompound (14) obtained in Example 9 is substituted for the compound (9),whereby a compound represented by Formula (25) can be obtained.

Example 21 Synthesis of Acetoxyethyl-HeptaisobutyloctasilsesquioxaneUsing the Compound (17) as a Raw Material

The same operation as in Example 17 is carried out, except that thecompound (17) obtained in Example 11 is substituted for the compound(9), whereby a compound represented by Formula (26) can be obtained.

Example 22 Synthesis of Acetoxyethyl-HeptaisooctyloctasilsesquioxaneUsing the Compound (18) as a Raw Material

The same operation as in Example 17 is carried out, except that thecompound (18) obtained in Example 13 is substituted for the compound(9), whereby a compound represented by Formula (27) can be obtained.

Example 23 Synthesis ofAcetoxyethyl-Heptatrifluoropropyloctasilsesquioxane Using the Compound(21) as a Raw Material

The compound (21) 22.71 g obtained in Example 15 and tetrahydrofuran(400 g) were introduced into a four neck flask of 500 ml equipped with areflux condenser, a thermometer and a rotator. Then,acetoxyethyltrichlorosilane (3.21 g, 1.6 equivalent based on thecompound (21)) was quickly added to a compound (21)/tetrahydrofuransolution, and the solution was stirred at a room temperature for 4hours. Then, after solid-liquid separation was carried out by filtrationthrough a filter, the filtrate was concentrated by means of a rotaryevaporator. Methanol (100 ml) was added to the concentrate to carry outsolid-liquid separation by filtration through a filter. Further,tetrahydrofuran (200 ml) was added to the solid component thus obtained,and the mixture was dried on anhydrous magnesium sulfate (5 g). Then,solid-liquid separation was carried out by filtration through a filter.Thereafter, methanol (100 g) was added to a solid component obtained byconcentrating the organic layer, and the solution was stirred under aroom temperature condition. Further, solid-liquid separation was carriedout by filtration through a filter, and a solid component obtained wasthen dried (75° C., 5 hours) under reduced pressure to obtain acolorless solid matter (12.2 g, yield: 51.6%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of ¹H-NMR, ¹³C-NMR and ²⁹Si-NMReach shown below that the colorless solid matter obtained had astructure represented by Formula (28).

¹H NMR (400 MHz, TMS standard: δ 0.0 ppm): 4.18 (t, 2H, —O—CH₂—), 2.14(m, 14H, —[CH₂]—CF₃), 2.04 (s, 3H, CH₃—(C═O)—), 1.19 (t, 2H, —CH₂—Si),095 (m, 14H, Si—[CH₂]—CH₂—CF₃)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 171.11 (C═O), 131.41,128.68, 125.92, 123.20 (—CF₃), 60.01 (—O—CH₂—), 28.17, 27.85, 27.55,27.25 (—[CH₂]—CF₃), 20.92 (CH₃—(C═O)—), 12.81 (—CH₂—Si), 4.03(Si—[CH₂]—CH₂—CF₃)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −68.66 (—CH₂—SiO_(1.5)),−67.62, −67.72 (CF₃—CH₂—CH₂—SiO_(1.5))

Example 24 Synthesis of Acetoxyethyl-Heptaphenyloctasilsesquioxane Usingthe Compound (29) as a Raw Material

A compound represented by Formula (29) (10 g, trisilanolphenyl POSS,manufactured by Hybrid Plastics U.S. Co., Ltd.), triethylamine (4.24 g,1.3 equivalent based on silanol) and tetrahydrofuran (200 ml) wereintroduced into a four neck flask of 500 ml equipped with a droppingfunnel, a reflux condenser, a thermometer and a rotator in an ice bath.

Then, acetoxyethyltrichlorosilane (3.32 g, 1.5 equivalent based on thecompound (29)) was quickly added to a compound (29)/tetrahydrofuransolution, and the solution was stirred at a room temperature for 2hours. Then, the reaction liquid was poured into hexane (1000 g). Asolid component deposited was recovered by suction filtration anddissolved again in toluene (90 g), and then the organic layer was washedwith water (330 ml). After washing was carried out three times, theorganic layer was separated and dried on anhydrous magnesium sulfate (5g). Subsequently, solid-liquid separation was carried out, by filtrationthrough a filter. Then, ethanol (90 g) was added to a solid componentobtained, and the mixture was stirred under a room temperaturecondition. Further, solid-liquid separation was carried out by means ofa pressure filtering device, and a solid component obtained was thendried (80° C., 3 hours) under reduced pressure to obtain a colorlesssolid matter (5.25 g, yield: 47.0%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of IR, ¹H-NMR, ¹³C-NMR and²⁹Si-NMR each shown below that the colorless solid matter obtained had astructure represented by Formula (22).

IR (KBr method: ν=1740 (C═O), 1430 (Si-Ph), 1240 (C—O) 1135 to 1090(Si-Ph), 1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, Ph-Si), 4.32 to 4.28 (t, 2H, —O—CH₂—), 1.84 (s, 3H,CH₃—(C═O)—), 1.37 to 1.33 (t, 2H, —CH₂—Si)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 171.15 (C═O), 134.4 to134.3, 131.1 to 131.0, 130.2, 128.12 (Ph-Si), 60.6 (—O—CH₂—), 20.8(CH₃—(C═O)—), 13.2 (—CH₂—Si)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −67.97 (—CH₂—SiO_(1.5)),−78.36, −78.67 (Ph-SiO_(1.5))

Example 25 Synthesis of Acetoxyethyl-HeptacyclohexyloctasilsesquioxaneUsing a Compound (30) as a Raw Material

The same operation as in Example 24 is carried out, except that acompound represented by Formula (30) (trisilanolcyclohexyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (23) described in Example 18 can beobtained.

Example 26 Synthesis of Acetoxyethyl-HeptacyclopentyloctasilsesquioxaneUsing a Compound (31) as a Raw Material

The same operation as in Example 24 is carried out, except that acompound represented by Formula (31) (trisilanolcyclopentyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.), is substituted for thecompound (29), whereby the compound (24) described in Example 19 can beobtained.

Example 27 Synthesis of Acetoxyethyl-Heptaethyloctasilsesquioxane Usinga Compound (32) as a Raw Material

The same operation as in Example 24 is carried out, except that acompound represented by Formula (32) (trisilanolethyl POSS, manufacturedby Hybrid Plastics, U.S. Co., Ltd.) is substituted for the compound(29), whereby the compound (25) described in Example 20 can be obtained.

Example 28 Synthesis of Acetoxyethyl-HeptaisobutyloctasilsesquioxaneUsing a Compound 33) as a Raw Material

The same operation as in Example 24 is carried out, except that acompound represented by Formula (33) (trisilanolisobutyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (26) described in Example 21 can beobtained.

Example 29 Synthesis of Acetoxyethyl-HeptaisooctyloctasilsesquioxaneUsing a Compound (34) as a Raw Material

The same operation as in Example 24 is carried out, except that acompound represented by Formula (34) (trisilanolisooctyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (27) described in Example 22 can beobtained.

Example 30 Synthesis of Silanol-ContainingHeptatrifluoropropylsilsesquioxane Using the Compound (21) as a RawMaterial

A four neck flask of 300 ml equipped with a dropping funnel, a refluxcondenser, a thermometer and a rotator was set in an ice bath. Thecompound (21) 5 g obtained in Example 15 was added to this four neckflask and dissolved in butyl acetate (50 g), and then acetic acid (0.5g) was dropwise added thereto. The flask was stirred for one hour as itwas put in the ice bath. After returned to a room temperature, thereaction liquid was washed (three times) with deionized water (100 ml).The solvent was distilled off by means of a rotary evaporator, and theresidue was dried (50° C., one hour) as it was under reduced pressure toobtain a viscous liquid (4.3 g). As a result of carrying out GPCmeasurement of the compound obtained, a single peak was shown, and thepresence of impurities was not confirmed. Further, analysis using IR wascarried out to result in confirming absorption (in the vicinity of 3400cm⁻¹) indicating the presence of a silanol group which was not observedin the compound (21). Accordingly, it was indicated that the compoundobtained had a structure represented by Formula (35).

Acetoxyethyltrichlorosilane is reacted with the compound (35) describedabove which is a starting raw material under the presence oftriethylamine according to the method described in Examples 24 to 29described above, whereby the compound (28) can be derived.

Example 31 Synthesis of Acetoxyethyl-Heptaphenyloctasilsesquioxane Usingthe Compound (9) as a Raw Material

The compound (9) 10 g obtained in Example 1, triethylamine (1.5 g) andtetrahydrofuran (200 ml) were introduced into a four neck flask of 500ml equipped with a reflux condenser, a thermometer and a rotator. Then,acetoxypropyltrichlorosilane (3.5 g, 1.5 equivalent based on thecompound (9)) was quickly added to a compound(9)/triethylamine/tetrahydrofuran solution, and the solution was stirredat a room temperature for 2 hours. Then, the reaction liquid was pouredinto hexane (1000 g). A solid component deposited was recovered bysuction filtration and dissolved again in toluene (90 g), and then theorganic layer was washed with water (330 ml). After washing was carriedout three times, the organic layer was separated and dried on anhydrousmagnesium sulfate (5 g). Subsequently, solid-liquid separation wascarried out by filtration through a filter. Then, ethanol (90 g) wasadded to a solid component obtained by concentrating the organic layer,and the mixture was stirred under a room temperature condition. Further,solid-liquid separation was carried out by means of a pressure filteringdevice, and a solid component obtained was then dried (80° C., 3 hours)under reduced pressure to obtain a colorless solid matter (7.15 g,yield: 67.6%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of IR, ¹H-NMR, ¹³C-NMR and²⁹Si-NMR each shown below that the white solid matter obtained had astructure represented by Formula (36).

IR (KBr method: ν=1740 (C═O), 1430 (Si-Ph), 1240 (C—O), 1135 to 1090(Si-Ph), 1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, [Ph]-Si), 4.07 to 4.04 (t, 2H, —O—[CH₂]—), 1.94 (s, 3H,[CH₃]—(C═O)—), 1.84 to 1.88 (tt, 2H, —CH₂—[CH₂]—CH₂—), 1.37 to 1.33 (t,2H, —[CH₂]—Si)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 171.10 (C═O), 134.4 to134.3, 131.1 to 131.0, 130.2, 128.12 (Ph-Si), 66.2 (—O—CH₂—), 22.2(—CH₂—[CH₂]—CH₂—), 20.9 ([CH₃]—(C═O)—), 8.26 (—[CH₂]—Si)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −65.30 (—CH₂—SiO_(1.5)),−78.26, −78.62 (Ph-SiO_(1.5))

Example 32 Synthesis of Acetoxypropyl-HeptacyclohexyloctasilsesquioxaneUsing the Compound (10) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (10) obtained in Example 5 is substituted for the compound (9),whereby a compound represented by Formula (37) can be obtained.

Example 33 Synthesis of Acetoxypropyl-HeptacyclopentyloctasilsesquioxaneUsing the Compound (13) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (13) obtained in Example 7 is substituted for the compound (9),whereby a compound represented by Formula (38) can be obtained.

Example 34 Synthesis of Acetoxypropyl-Heptaethyloctasilsesquioxane Usingthe Compound (14) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (14) obtained in Example 9 is substituted for the compound (9),whereby a compound represented by Formula (39) can be obtained.

Example 35 Synthesis of Acetoxypropyl-HeptaisobutyloctasilsesquioxaneUsing the Compound (17) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (17) obtained in Example 11 is substituted for the compound(9), whereby a compound represented by Formula (40) can be obtained.

Example 36 Synthesis of Acetoxypropyl-HeptaisooctyloctasilsesquioxaneUsing the Compound (18) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (18) obtained in Example 13 is substituted for the compound(9), whereby a compound represented by Formula (41) can be obtained.

Example 37 Synthesis ofAcetoxypropyl-Heptatrifluoropropyloctasilsesquioxane Using the Compound(21) as a Raw Material

The same operations as the reaction conditions described in Example 31and the refining conditions described in Example 23 are carried out,except that the compound (21) obtained in Example 15 is substituted forthe compound (9), whereby a compound represented by Formula (42) can beobtained.

Example 38 Synthesis of Acetoxypropyl-HeptaphenyloctasilsesquioxaneUsing the Compound (29) as a Raw Material

The compound (36) described in Example 31 can be obtained by a method inwhich acetoxypropyl-trichlorosilane (1.5 equivalent based on thecompound (29)) is reacted with the compound (trisilanolphenyl POSS,manufactured by Hybrid Plastics U.S. Co., Ltd.) represented by Formula(29) described in Example 24 used as a raw material in tetrahydrofuranunder the presence of triethylamine (1.3 equivalent based on silanol).

Example 39 Synthesis of Acetoxypropyl-HeptacyclohexyloctasilsesquioxaneUsing the Compound (30) as a Raw Material

The same operation as in Example 38 is carried out, except that thecompound represented by Formula (30) (trisilanolcyclohexyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (37) described in Example 32 can beobtained.

Example 40 Synthesis of Acetoxypropyl-HeptacyclopentyloctasilsesquioxaneUsing the Compound (31) as a Raw Material

The same operation as in Example 38 is carried out, except that thecompound represented by Formula (31) (trisilanolcyclopentyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (38) described in Example 33 can beobtained.

Example 41 Synthesis of Acetoxypropyl-Heptaethyloctasilsesquioxane Usingthe Compound (32) as Raw Material

The same operation as in Example 38 is carried out, except that thecompound represented by Formula (32) (trisilanolcycloethyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (39) described in Example 34 can beobtained.

Example 42 Synthesis of Acetoxypropyl-HeptaisobutyloctasilsesquioxaneUsing the Compound (33) as Raw Material

The same operation as in Example 38 is carried out, except that thecompound represented by Formula (33) (trisilanolisobutyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (40) described in Example 35 can beobtained.

Example 43 Synthesis of Acetoxypropyl-HeptaisooctyloctasilsesquioxaneUsing the Compound (34) as Raw Material

The same operation as in Example 38 is carried out, except that thecompound represented by Formula (34) (trisilanolisooctyl POSS,manufactured by Hybrid Plastics, U.S. Co., Ltd.) is substituted for thecompound (29), whereby the compound (41) described in Example 36 can beobtained.

Example 44 Synthesis ofAcetoxypropyl-Heptatrifluoropropyloctasilsesquioxane Using the Compound(35) as a Raw Material

Acetoxyethyltrichlorosilane is reacted under the presence oftriethylamine according to the method described in Examples 31 to 43described above, except that the compound represented by Formula (35) issubstituted for the compound (29), whereby the compound (42) describedin Example 37 can be obtained.

Example 45 Synthesis of Hydroxyethyl-Heptaphenyloctasilsesquioxane Usingthe Compound (22) as a Raw Material

The compound (22) 2.58 g obtained in Example 17 was introduced into aKjeldahl flask of 500 ml equipped with a rotator, and a mixed solution(300 ml) of methanol (174.7 ml), chloroform (174.3 ml) and sulfuric acid(36N, 0.7 ml) was introduced thereinto and stirred for 72 hours under aroom temperature condition. Then, the solution was concentrated by meansof a rotary evaporator, and the concentrate was dissolved again in ethylacetate (500 ml). Thereafter, the organic layer was washed with water(500 ml) in a separating funnel and dried on anhydrous magnesium sulfate(5 g). Solid-liquid separation was carried out by filtration through afilter, and then the organic layer was concentrated by means of a rotaryevaporator and dried to obtain a colorless solid matter (2.37 g, yield:91.7%). The colorless solid matter (1.09 g) was recrystallized fromtoluene, and toluene was distilled off under reduced pressure to obtaina colorless solid matter (0.48 g, yield: 43.7%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of IR, ¹H-NMR, ¹³C-NMR and²⁹Si-NMR each shown below that the solid matter had a structurerepresented by Formula (43).

IR (KBr method: ν=3600 to 3200 (OH), 1420 (Si-Ph) 1135 to 1090 (Si-Ph),1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, Ph-Si), 3.85 to 3.87 (t, 2H, —CH₂—O—), 1.42 to 1.62 (broad, 1H,—OH), 1.26 to 1.31 (t, 2H, Si—CH₂—)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 134.5 to 134.1, 131.1 to131.0, 130.3, 128.11 to 127.9 (Ph-Si), 58.6 (—CH₂—OH), 17.5 (Si—CH₂—)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −67.31 (—CH₂—SiO_(1.5)),−78.42, −78.79 (Ph-SiO_(1.5))

The compound (22) obtained in Example 24 can be derived as well into thecompound (43) by carrying out the same operation as described above.

Example 46 Synthesis of Hydroxyethyl-Heptaphenyloctasilsesquioxane Usingthe Compound (22) as a Raw Material

Reaction was carried out according to Example 45 to obtain a colorlesssolid matter (0.09 g, yield: 94.7%), except that the conditions werechanged to the compound (22) 0.1 g obtained in Example 17, methanol(66.6 ml), chloroform (100 ml) and sulfuric acid (36N, 0.3 ml). It wasfound from the results of IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR each shownbelow that the solid matter obtained had the structure represented byFormula (43).

IR (KBr method: ν=3600 to 3200 (OR), 1420 (Si-Ph), 1135 to 1090 (Si-Ph),1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, Ph-Si), 3.85 to 3.87 (t, 2H, —CH₂—O—), 1.42 to 1.62 (broad, 1H,—OH), 1.26 to 1.31 (t, 2H, Si—CH₂—)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 134.5 to 134.1, 131.1 to131.0, 130.3, 128.11 to 127.9 (Ph-Si), 58.6 (—CH₂—OH), 17.5 (Si—CH₂—)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −67.31 (—CH₂—SiO_(1.5)),−78.42, −78.79 (Ph-SiO_(1.5))

The compound (22) obtained in Example 22 can be derived as well into thecompound (43) by carrying out the same operation as described above.

Example 47 Transesterification Reaction of the Compound (22) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 2 to obtain a colorlesssolid matter (0.064 g, yield: 67.4%), except that the conditions werechanged to the compound (22) 0.1 g obtained in Example 17, ethanol (83.3ml), chloroform (83.3 ml) and sulfuric acid (36N, 0.3 ml). IRmeasurement was carried out, and as a result thereof, absorption ofcarbonyl based on the presence of an acetoxy group was observed in 1740cm⁻¹. It was found from the results of ¹H-NMR that the solid matter wasa mixture (content of the compound (43): 66.3 mol %) of the compound(43) and the compound (22).

Example 48 Transesterification Reaction of the Compound (22) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 2 to obtain a colorlesssolid matter 0.078 g, yield: 82.1%), except that the conditions werechanged to the compound (22) 0.1 g obtained in Example 17, ethanol (66.6ml), chloroform (100 ml), sulfuric acid (36N, 0.3 ml) and the reactiontime: 96 hours. IR measurement was carried out, and as a result thereof,absorption of carbonyl based on the presence of an acetoxy group wasobserved in 1740 cm⁻¹. It was found from the results of ¹H-NMR that thesolid matter was a mixture (content of the compound (43): 90.1 mol %) ofthe compound (43) and the compound (22).

Example 49 Synthesis of Hydroxyethyl-HeptacyclohexyloctasilsesquioxaneUsing the Compound (23) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (23) obtained in Example 18 or Example 25 is substituted forthe compound (22), whereby a compound represented by Formula (44) can beobtained.

Example 50 Synthesis of Hydroxyethyl-HeptacyclopentyloctasilsesquioxaneUsing the Compound (24) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (24) obtained in Example 19 or Example 26 is substituted forthe compound (22), whereby a compound represented by Formula (45) can beobtained.

Example 51 Synthesis of Hydroxyethyl-Heptaethyloctasilsesquioxane Usingthe Compound (25) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (25) obtained in Example 20 or Example 27 is substituted forthe compound (22), whereby a compound represented by Formula (46) can beobtained.

Example 52 Synthesis of Hydroxyethyl-HeptaisobutyloctasilsesquioxaneUsing the Compound (26) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (26) obtained in Example 21 or Example 28 is substituted forthe compound (22), whereby a compound represented by Formula (47) can beobtained

Example 53 Synthesis of Hydroxyethyl-HeptaisooctyloctasilsesquioxaneUsing the Compound (27) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (27) obtained in Example 27 or Example 29 is substituted forthe compound (22), whereby a compound represented by Formula (48) can beobtained.

Example 54 Synthesis ofHydroxyethyl-Heptatrifluoropropyloctasilsesquioxane Using the Compound(28) as a Raw Material

The compound (28) 3.5 g obtained in Example 23 was introduced into athree neck flask of 1000 ml equipped with a reflux condenser, athermometer and a rotator, and a mixed solution (600 ml) of methanol(359.5 ml), AK-225 (239.6 ml, HCFC-225 CF₃CF₂CHCl₂/CClF₂CF₂CHClFmixture, manufactured by Asahi Glass Co., Ltd.) and sulfuric acid (36N,0.7 ml) was introduced thereinto and stirred at a room temperature for12 hours. Thereafter, the temperature was raised up to 45° C., and thesolution was further stirred for 9 hours. Then, the solution wasconcentrated by means of a rotary evaporator, and the concentrate wasdissolved again in AK-225 (200 ml). Thereafter, the organic layer waswashed with water (500 ml) in a separating funnel and dried on anhydrousmagnesium sulfate (5 g). Solid-liquid separation was carried out byfiltration through a filter, and then the organic layer was concentratedby means of a rotary evaporator and dried to obtain a colorless solidmatter (3.04 g, yield: 89.9%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR each shown below that the colorless solid matter obtained had thestructure represented by Formula (43).

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 3.81 (t, 2H, —CH₂—O—), 2.14(m, 14H, —[CH₂]—CF₃), 1.39 (broad, 1H, —OH), 1.13 (t, 2H,Si—[CH₂]—CH₂—OH), 0.93 (m, 14H, Si—[CH₂]—CH₂—CF₃)

¹³C NMR (100 MHz, TMS standard: δ 0.0 ppm): 131.31, 128.58, 125.83,123.11 (—CF₃), 58.08 (—CH₂—OH), 28.12, 27.83, 27.52, 27.22 (—[CH₂]—CF₃),19.74 (—CH₂—Si), 4.02 (Si—[CH₂]—CH₂—CF₃)

²⁹Si (79 MHz, TMS standard: δ=0.0 ppm): −67.84 (—CH₂—SiO_(1.5)), −67.65,−67.66, −67.84 (CF₃—CH₂—CH₂—SiO_(1.5))

The compound (28) obtained in Example 30 can be derived as well into thecompound (49) by carrying out the same operation as described above.

Example 55 Transesterification Reaction of the Compound (2.8) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 54 to obtain a colorlesssolid matter (yield: 93.1%), except that the conditions were changed tothe compound (28) 0.5 g obtained in Example 23, methanol (42.7 ml),AK-225 (42.7 ml) and sulfuric acid (36N, 0.26 ml). It was found from theresults of ¹H-NMR that the solid matter was a mixture (content of thecompound (49): 89.4 mol %) of the compound (49) and the compound (28).

Example 56 Transesterification Reaction of the Compound (28) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 54 to obtain a colorlesssolid matter (yield: 92.2%), except that the conditions were changed tothe compound (28) 0.5 g obtained in Example 23, methanol (42.7 ml),AK-225 (42.7 ml), sulfuric acid (36N, 0.26 ml), a reaction temperatureof a room temperature and a reaction time of 72 hours. It was found fromthe results of ¹H-NMR that the solid matter was a mixture (content ofthe compound (49): 91.3 mol %) of the compound (49) and the compound(28).

Example 57 Transesterification Reaction of the Compound (28) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 54 to obtain a colorlesssolid matter (yield: 91.0%), except that the conditions were changed tothe compound (28) 0.5 g obtained in Example 23, methanol (42.7 ml),chloroform (42.7 ml), sulfuric acid (36N, 0.26 ml), a reactiontemperature of a room temperature and a reaction time of 72 hours. Itwas found from the results of ¹H-NMR that the solid matter was a mixture(content of the compound (49): 81.5 mol %) of the compound (49) and thecompound (28).

Example 58 Transesterification Reaction of the Compound (28) by aChloroform/Methanol/Sulfuric Acid Mixed Solvent System

Reaction was carried out according to Example 54 to obtain a colorlesssolid matter (yield: 90.9%), except that the conditions were changed tothe compound (28) 0.5 g obtained in Example 23, methanol (42.7 ml),chloroform (42.7 ml), p-toluenesulfonic acid (4.43 g), a reactiontemperature of a room temperature and a reaction time of 72 hours. Itwas found from the results of ¹H-NMR that the solid matter was a mixture(content of the compound (49): 89.0 mol %) of the compound (49) and thecompound (28).

Example 59 Synthesis of Hydroxypropyl-HeptaphenyloctasilsesquioxaneUsing the Compound (36) as a Raw Material

The compound (36) 2.5 g obtained in Example 31 was introduced into aKjeldahl flask of 500 ml equipped with a rotator, and a mixed solution(417.4 ml) of methanol (208.3 ml), chloroform 208.3 ml) and sulfuricacid (36N, 0.75 ml) was introduced thereinto and stirred for 72 hoursunder a room temperature condition. Then, the solution was concentratedby means of a rotary evaporator, and the concentrate was dissolved againin ethyl acetate (500 ml). Thereafter, the organic layer was washed withwater (500 ml) in a separating funnel and dried on anhydrous magnesiumsulfate (5.0 g). Solid-liquid separation was carried out by filtrationthrough a filter, and then the organic layer was concentrated by meansof a rotary evaporator and dried to obtain a colorless solid matter(2.35 g, yield: 97.9%). The colorless solid matter was washed withethanol to obtain a colorless solid matter (1.26 g, yield: 52.5%) bysuction filtration.

As a result of carrying out GPC measurement of the compound, a singlepeak was confirmed, and the presence of impurities was not confirmed. Itwas found from the results of IR, ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR eachshown below that the solid matter had a structure represented by Formula(50).

IR (KBr method: ν=3600 to 3200 (OH), 1420 (Si-Ph), 1135 to 1090 (Si-Ph),1090 to 1000 (Si—O—Si) cm⁻¹

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.48 to 7.32(m, 35H, [Ph]-Si), 3.62 to 3.57 (t, 2H, —[CH₂]—O—), 1.2 (broad, 1H,—[OH]), 1.78 to 1.74 (tt, 2H, —CH₂—[CH₂]—CH₂—), 0.90 to 0.86 (t, 2H,Si—[CH₂]—)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 134.5 to 134.4, 131.1 to131.0, 130.6 to 130.4, 128.2 to 128.1 ([Ph]-Si), 65.0 (—[CH₂]—OH), 26.1(—CH₂—[CH₂]—CH₂—), 7.9 (Si—[CH₂]—)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −65.08 (—CH₂—SiO_(1.5)),−78.55, −78.94 (Ph-SiO_(1.5))

The compound (36) obtained in Example 38 can be derived as well into thecompound (50) by carrying out the same operation as described above.

Example 60 Synthesis of Hydroxypropyl-HeptacyclohexyloctasilsesquioxaneUsing the Compound (37) as a Raw Material

The same operation as in Example 59 is carried out, except that thecompound (37) obtained in Example 32 or Example 39 is substituted forthe compound (36), whereby a compound represented by Formula (51) can beobtained.

Example 61 Synthesis of Hydroxypropyl-HeptacyclopentyloctasilsesquioxaneUsing the Compound (38) as a Raw Material

The same operation as in Example 59 is carried out, except that thecompound (38) obtained in Example 33 or Example 40 is substituted forthe compound (36), whereby a compound represented by Formula (52) can beobtained.

Example 62 Synthesis of Hydroxypropyl-Heptaethyloctasilsesquioxane Usingthe Compound (39) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (39) obtained in Example 34 or Example 41 is substituted forthe compound (36), whereby a compound represented by Formula (53) can beobtained.

Example 63 Synthesis of Hydroxypropyl-HeptaisobutyloctasilsesquioxaneUsing the Compound (40) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (40) obtained in Example 35 or Example 42 is substituted forthe compound (36), whereby a compound represented by Formula (54) can beobtained.

Example 64 Synthesis of Hydroxyethyl-HeptaisooctyloctasilsesquioxaneUsing the Compound (41) as a Raw Material

The same operation as in Example 45 is carried out, except that thecompound (41) obtained in Example 36 or Example 43 is substituted forthe compound (36), whereby a compound represented by Formula (55) can beobtained.

Example 65 Synthesis of Hydroxyethyl-HeptatrifluoropropylsilsesquioxaneUsing the Compound (42) as a Raw Material

The same operation as in Example 54 is carried out, except that thecompound (42) obtained in Example 37 or Example 44 is substituted forthe compound (36), whereby a compound represented by Formula (56) can beobtained.

Example 66 Synthesis of Sodium-Bondedtridecafluoro-1,1,2,2-tetrahydrooctylsilsesquioxane Compound Usingtridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane as a Raw Material

A four neck flask having a content volume of 50 ml equipped with areflux condenser, a thermometer and a dropping funnel was charged withtridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (4.9 g), THF (15ml), sodium hydroxide (0.2 g) and ion-exchanged water (0.2 g), and arotator was put thereinto to heat and reflux the mixture at 75° C.Stirring was continued for 5 hours since refluxing was started to finishthe reaction. Then, it was concentrated under constant pressure byheating and dried at 80° C. for 3 hours in a vacuum dryer to obtain 4.0g of a viscous liquid.

Example 67 Introduction of Trimethylsilyl Group

A three neck flask having a content volume of 50 ml was charged with thepower-like solid matter (2.6 g) described above, THF (10 g),triethylamine (1.0 g) and trimethylchlorosilane (3.3 g), and the mixturewas stirred at a room temperature for 3 hours while stirring by means ofa magnetic stirrer. After finishing the reaction, the same treatment asin confirming the structure in Example 16 was carried out to obtain 1.3g of a viscous liquid.

The compound thus obtained was analyzed by GPC. As a result of carryingout the measurement, it was confirmed that the viscous liquid wasmonodispersed and that it had a weight average molecular weight of 3650in terms of polystyrene and a purity of 100%. Synthetically judging fromthe above results and the results obtained in Examples 3 to 16, it wasestimated that the viscous liquid which was the object of the analysiswas a silicon compound represented by Formula (57). Accordingly, it isindicated that the compound obtained in Example 66 has a structurerepresented by Formula (58).

Example 68 Synthesis of Silanol-Containingtridecafluoro-1,1,2,2-tetrahydrooctylsilsesquioxane Compound Using theCompound (58) as a Raw Material

The same operation as in Example 30 is carried out, except that thecompound (58) is used as a raw material and that AK-225 is used as thesolvent used for the reaction in place of butyl acetate, whereby acompound represented by Formula (59) can be obtained.

Example 69 Synthesis ofacetoxyethyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (58) as a Raw Material

The same operation as in Example 23 is carried out, except that thecompound (58) is used as a raw material and that AK-225 is used as thesolvent used for the reaction in place of tetrahydrofuran, whereby acompound represented by Formula (60) can be obtained.

Example 70 Synthesis ofacetoxypropyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (58) as a Raw Material

The same operation as in Example 31 is carried out, except that thecompound (58) is used as a raw material and that AK-225 is used as thesolvent used for the reaction in place of tetrahydrofuran, whereby acompound represented by Formula (61) can be obtained.

Example 71 Synthesis ofacetoxyethyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (59) as a Raw Material

Acetoxyethyltrichlorosilane is reacted under the presence oftriethylamine according to the method described in Examples 24 to 30,except that the compound (59) is used as a raw material and that thesolvent used for the reaction is changed to AK-225, whereby the compound(60) can be derived.

Example 72 Synthesis ofacetoxypropyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (59) as a Raw Material

Acetoxypropyltrichlorosilane is reacted under the presence oftriethylamine according to the method described in Examples 38 to 44,except that the compound (59) is used as a raw material and that thesolvent used for the reaction is changed to AK-225, whereby the compound(61) can be derived.

Example 73 Synthesis ofhydroxyethyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (60) as a Raw Material

The same operation as in Examples 54 to 58 is carried out, except thatthe compound (66) obtained in Example 69 or Example 71 is used, wherebya compound represented by Formula (62) can be obtained.

Example 74 Synthesis ofhydroxypropyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxaneUsing the Compound (61) as a Raw Material

The same operation as in Examples 54 to 58 is carried but, except thatthe compound (61) obtained in Example 70 or Example 72 is used, wherebya compound represented by Formula (63) can be obtained.

Example 75 Compound (64) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptaphenyloctasilsesquioxane

A 25 ml-Kjeldahl flask was charged with the compound (43) (1.21 g),triethylamine (0.12 g) dried on molecular sieves (4 A) and dry methylenechloride (6.41 g) under argon atmosphere. The compound C was dissolvedwhile stirring at a room temperature by means of a magnetic stirrer, andthen the solution was cooled on a dry ice-methanol bath to maintain asolution temperature at −78° C. Then, 2-bromo-2-methylpropionyl bromide(0.3 g, 1.1 equivalent based on the compound (43)) was quickly added tothe above solution and stirred at −78° C. for one hour, and then thesolution was further stirred at a room temperature for 2 hours. Afterfinishing the reaction, a triethylamine-hydrobromic acid salt wasremoved by filtration. Methylene chloride (100 ml) was added to thereaction liquid obtained, and it was washed in order once with water(300 ml), twice with a sodium hydrogencarbonate aqueous solution (1%,300 ml) and twice with water (300 ml) and then dried on anhydrousmagnesium sulfate (5 g). Thereafter, the above liquid was concentratedat a room temperature by means of a rotary evaporator to reduce a liquidamount to about 20 ml. Methanol (400 ml) was added to this concentrate(20 ml) to deposit a solid component. Then, it was left standing stillin a freezing chamber of −35° C. to sufficiently deposit the solidcomponent, and then solid-liquid separation was carried out byfiltration. The solid component thus obtained was dried (40° C., 6hours) under reduced pressure to obtain a white solid matter (1.13 g,yield: 81.4%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was confirmed from the measuring result of the massanalytical spectrum that the absolute molecular weight was consistentwith a theoretical molecular weight of a structure represented byFormula (64). It was found from the results of IR, ¹H-NMR, ¹³C-NMR and²⁹Si-NMR each shown below that the white solid matter obtained had astructure represented by Formula (64).

IR (KBr method: ν=1740 (C═O) 1430 (Si-Ph), 1270 (C—O), 1135 to 1090(Si-Ph), 1090 to 1000 (Si—O—Si) cm⁻¹.

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.46 to 7.31(m, 35H, Ph-Si), 4.41 to 4.37 (t, 2H, —O—CH₂—), 1.79 (s, 6H,—C(Br)(CH₃)₂), 1.43 to 1.39 (t, 2H, —CH₂—Si).

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 171.7 (C═O), 134.3, 131.1 to131.1, 131.2 to 130.1, 128.1 to 128.0 (Ph-Si), 62.5 (—CH₂—O—), 55.8(—C(Br)), 30.6 ((—CH₃)₂), 12.9 (Si—CH₂—).

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −68.27 (—CH₂—SiO_(1.5)),−78.4, −78.7 (Ph-SiO_(1.5)).

Example 76 Compound (65) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptacyclohexyloctasilsesquioxane

The same operation as in Example 75 is carried out, except that thecompound (44) obtained in Example 49 is substituted for the compound(43), whereby a compound represented by Formula (65) can be obtained.

Example 77 Compound (66) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptacyclopentyloctasilsesquioxane

The same operation as in Example 75 is carried out, except that thecompound (45) obtained in Example 50 is substituted for the compound(43), whereby a compound represented by Formula (66) can be obtained.

Example 78 Compound (67) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptaethyloctasilsesquioxane

The same operation as in Example 75 is carried out, except that thecompound (46) obtained in Example 51 is substituted for the compound(43), whereby a compound represented by Formula (67) can be obtained.

Example 79 Compound (68) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptaisobutyloctasilsesquioxane

The same operation as in Example 75 is carried out, except that thecompound (47) obtained in Example 52 is substituted for the compound(43), whereby a compound represented by Formula (68) can be obtained.

Example 80 Compound (69) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptaisooctyloctasilsesquioxane

The same operation as in Example 75 is carried out, except that thecompound (48) obtained in Example 53 is substituted for the compound(43), whereby a compound represented by Formula (69) can be obtained

Example 81 Compound (70) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-heptatrifluoropropyloctasilsesquioxane

A 25 ml-Kjeldahl flask was charged with the compound (49) (0.29 g),triethylamine (0.05 g) dried on molecular sieves (4 A) and dry methylenechloride (6.66 g) under argon atmosphere. The compound (49) wasdissolved therein while stirring at a room temperature by means of amagnetic stirrer, and then the solution was cooled on a dry ice-methanolbath to maintain a solution temperature at −78° C. Then,2-bromo-2-methylpropionyl bromide (0.12 g, 2.0 equivalent based on thecompound (49)) was quickly added to the above solution and stirred at−78° C. for one hour, and then the solution was further stirred at aroom temperature for 2 hours. After finishing the reaction, atriethylamine-hydrobromic acid salt was removed by filtration. Methylenechloride (100 ml) was added to the reaction liquid obtained, and it waswashed in order once with water (300 ml), twice with a sodiumhydrogencarbonate aqueous solution (1%, 300 ml) and twice with water(300 ml) and then dried on anhydrous magnesium sulfate (5 g).Thereafter, the above liquid was concentrated at a room temperature bymeans of a rotary evaporator to reduce a liquid amount to about 20 ml.Toluene (400 ml) was added to this concentrate (20 ml) to deposit asolid component. Then, it was left standing still in a freezing chamberof −35° C. to sufficiently deposit the solid component, and thensolid-liquid separation was carried out by filtration. The solidcomponent thus obtained was dried (40° C., 6 hours) under reducedpressure to obtain a white solid matter (0.17 g, yield: 60%).

As a result of carrying out GPC measurement of the compound obtained, asingle peak was confirmed, and the presence of impurities was notconfirmed. It was found from the results of ¹H-NMR, ¹³C-NMR and ²⁹Si-NMR each shown below that the white solid matter obtained had astructure represented by Formula (70).

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 4.28 (t, 2H, —O—CH₂—), 2.15(m, 14H, —[CH₂]—CF₃), 1.93 (s, 6H, —C(Br)(CH₃)₂), 1.25 (t, 2H,Si—(CH₂—CH₂—O—), 0.94 (m, 14H, Si—[CH₂]—CH₂—CF₃)

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 171.23 (C═O), 131.32,128.57, 125.79, 123.07 (—CF₃), 61.83 (—CH₂—O—), 55.80 (—C(Br)), 30.70((—CH₃)₂), 28.13, 27.83, 27.52, 27.23 (—[CH₂]—CF₃), 12.45(Si—[CH₂]—CH₂—O—), 4.00 (Si—[CH₂]—CH₂—CF₃)

²⁹Si NMR (79 MHz, TMS standard: δ=0.0 ppm): −69.02 (—CH₂—SiO_(1.5)),−67.67, −67.73 (CF₃—CH₂—CH₂—SiO_(1.5))

Example 82 Compound (71) Synthesis of(2-bromo-2-methylpropionyloxyethyl)-hydroxyethyl-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxane

The same operation as in Example 81 is carried out, except that thecompound (62) obtained in Example 73 is substituted for the compound(43) and that methylene chloride is changed to AK-225, whereby acompound represented by Formula (71) can be obtained.

Example 83 Compound (72) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptaphenyloctasilsesquioxane

A 100 ml-Kjeldahl flask was charged with the compound (50) (2.0 g)obtained by the method shown in Example 59, triethylamine (0.3 g) driedon molecular sieves (4 A) and dry methylene chloride (38 g) under argonatmosphere. The compound (50) was dissolved therein while stirring at aroom temperature by means of a magnetic stirrer, and then the solutionwas cooled on a dry ice-methanol bath to maintain a solution temperatureat −78° C. Then, 2-bromo-2-methylpropionyl bromide (0.68 g, 1.5equivalent based on the compound (50)) was quickly added to the abovesolution and stirred at −78° C. for one hour, and then the solution wasfurther stirred at a room temperature for 2 hours. After finishing thereaction, a triethylamine-hydrobromic acid salt was removed byfiltration. Methylene chloride (100 ml) was added to the reaction liquidobtained, and it was washed in order once with water (300 ml), twicewith a sodium hydrogencarbonate aqueous solution (1%, 300 ml) and twicewith water (300 ml) and then dried on anhydrous magnesium sulfate (5 g).Thereafter, the above liquid was concentrated at a room temperature bymeans of a rotary evaporator to reduce a liquid amount to about 20 ml.Methanol (400 ml) was added to this concentrate (20 ml) to deposit asolid component. Then, it was left standing still in a freezing chamberof −35° C. to thereby sufficiently deposit the solid component, and thensolid-liquid separation was carried out by filtration. The solidcomponent thus obtained was dried (40° C., 6 hours) under reducedpressure to obtain a white solid matter (1.1 g, yield: 48.0%).

As a result of carrying out GPC measurement of the white solid matterobtained, a single peak was confirmed, and the presence of impuritieswas not confirmed. It was found from the results of IR, ¹H-NMR, ¹³C-NMRand ²⁹Si-NMR each shown below that the white solid matter obtained had astructure represented by Formula (72).

IR (KBr method: ν=1740 (C═O), 1430 (Si-Ph), 1270 (C—O), 1135 to 1090(Si-Ph), 1090 to 1000 (Si—O—Si) cm⁻¹.

¹H NMR (400 MHz, TMS standard: δ=0.0 ppm): 7.82 to 7.72, 7.49 to 7.33(m, 35H, Ph-Si), 4.17 to 4.14 (t, 2H, —O—CH₂—), 1.92 to 1.88 (t, 2H,—CH₂—[CH₂]—CH₂—), 1.79 (s, 6H, —C(Br)(CH₃)₂, 0.96 to 0.91 (t, 2H,—CH₂—Si).

¹³C NMR (100 MHz, TMS standard: δ=0.0 ppm): 172.1 (C═O), 13.4.7 to134.6, 131.3, 130.7 to 130.6, 128.4 to 128.3 (Ph-Si), 68.0 (—CH₂—O—)56.3 (—C(Br)), 31.1 ((—CH₃)₂), 22.4 (—CH₂—[CH₂]—CH₂—), 8.4 (Si—CH₂—).

²⁹Si NMR (79 MHz, TMS standard: δ 0.0 ppm): −65.58 (—CH₂—SiO_(1.5)),—78.46, −78.80 (Ph-SiO_(1.5)).

Example 84 Compound (73) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptacyclohexyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (51) obtained in Example 60 is substituted for the compound(50), whereby a compound represented by Formula (73) can be obtained.

Example 85 Compound (74) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptacyclopentyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (52) obtained in Example 61 is substituted for the compound(50), whereby a compound represented by Formula (74) can be obtained.

Example 86 Compound (75) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptaethyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (53) obtained in Example 62 is substituted for the compound(50), whereby a compound represented by Formula (75) can be obtained.

Example 87 Compound (76) (Synthesis of2-bromo-2-methylpropionyloxypropyl)-heptaisobutyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (54) obtained in Example 63 is substituted for the compound(50), whereby a compound represented by Formula (76) can be obtained.

Example 88 Compound (77) Synthesis of(2-bromo-2-ethylpropionyloxypropyl)-heptaisooctyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (55) obtained in Example 64 is substituted for the compound(50), whereby a compound represented by Formula (77) can be obtained.

Example 89 Compound (78) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptatrifluoropropyloctasilsesquioxane

The same operation as in Example 83 is carried out, except that thecompound (56) obtained in Example 65 is substituted for the compound(50), whereby a compound represented by Formula (78) can be obtained.

Example 90 Compound (79) Synthesis of(2-bromo-2-methylpropionyloxypropyl)-heptamidecafluoro-1,1,2,2-tetrahydrooctyloctasilsesquioxane

The same operation as in Example 81 is carried out, except that thecompound (63) obtained in Example 74 is substituted for the compound(50) and that methylene chloride is changed to AK-225, whereby acompound represented by Formula (79) can be obtained.

Example 91 Preparation of Solution for Polymerization

Cuprous bromide was introduced into a heat resistant glass-made ampul ina draft which was cut off from a UV ray, and a compound(64)/styrene/L-(−)-sparteine/diphenyl ether solution was further addedthereto and quickly cooled using liquid nitrogen. Then, freezing vacuumdeaeration (pressure: 1.0 Pa) was carried out three times by means of avacuum device equipped with an oil-sealed rotary pump, and the ampul wasquickly sealed by means of a hand burner while maintaining a state ofvacuum. In this case, a proportion of the compound (64), styrene,cuprous bromide and L-(−)-sparteine in the above solution forpolymerization was set to 1:500:1:2 in terms of a mole ratio in theabove order, and a use amount of diphenyl ether was set to such anamount that a concentration of styrene became 50 wt %.

<Polymerization>

The sealed heat resistant glass-made ampul was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (1a). In this case, thepolymerization temperature was 110° C., and the polymerization time was1.0 hour. Thereafter, a prescribed amount of the solution of the polymer(1a) was sampled and diluted with tetrahydrofuran, and then it wassubjected to GPC measurement. A monomer conversion rate in thispolymerization reaction system was analyzed based on a peak areaobtained from a GPC measured value of a polystyrene solution having aknown concentration. The polymer obtained was reprecipitated and refinedusing methanol. Then, a tetrahydrofuran solution (1 wt %) of the abovepolymer was prepared, and this was allowed to pass through a columnfilled with activated carbon to thereby remove the copper complex byadsorption. Further, this solution was dropwise added to methanol toreprecipitate the polymer, and this was dried (80° C., 6 hours) underreduced pressure. Shown in Table 10 are the analytical results of themonomer conversion rate and a theoretical number average molecularweight, a number average molecular weight and a molecular weightdistribution of the polymer (1a).

Examples 92 to 100

Polymerization was carried out in the same manner as in Example 91 toobtain the respective brown viscous solutions of a polymer (1b) to apolymer (1j), except that the polymerization time was changed as shownin Table 10. Then, the monomer conversion rates were determined in thesame manner as in the case of Example 91, and the respective polymerswere refined in the same manner as in the case of Example 91 todetermine a theoretical number average molecular weight, a numberaverage molecular weight and a molecular weight distribution of thepolymers. The results thereof are shown in Table 10.

TABLE 10 Polymerization Mn Mn Molecular weight Example Example timeConversion teoretical measured distribution No. No. (hr) (mol-%) valuevalue (Mw/Mn) 91 1a 1.0 6.1 4,300 3,700 1.14 92 1b 2.0 12.3 7,600 7,6001.11 93 1c 3.2 17.8 10,400 11,400 1.09 94 1d 3.7 22.5 12,900 13,200 1.1195 1e 4.0 29.1 16,300 17,000 1.11 96 1f 5.0 28.9 16,200 17,000 1.14 971g 6.5 34.9 19,300 20,700 1.15 98 1h 9.0 45.9 25,100 24,900 1.20 99 1i13.0 64.1 34,000 36,500 1.23 100 1j 18.0 75.7 40,600 45,000 1.30

Polymers can be obtained by the methods according to the examplesdescribed above using the compounds (65) to (69) in place of thecompound (65).

Example 101 Preparation of Solution for Polymerization

Cuprous bromide was introduced into a heat resistant glass-made ampul ina draft which was cut off from a UV ray, and a compound (64)/methylmethacrylate/L-(−)-sparteine/anisole solution was further added theretoand quickly cooled using liquid nitrogen. Then, freezing vacuumdeaeration (pressure: 1.0 Pa) was carried out three times by means of avacuum device equipped with an oil-sealed rotary pump, and the ampul wasquickly sealed by means of a hand burner while maintaining a state ofvacuum. In this case, a proportion of the compound (64), methylmethacrylate, cuprous bromide and L-(−)-sparteine in the above solutionfor polymerization was set to 1:500:0.5:1 in terms of a mole ratio inthe above order, and a use amount of anisole was set to such an amountthat a concentration of methyl methacrylate became 25 wt %.

<Polymerization>

The sealed heat resistant glass-made ampul was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (2a). In this case, thepolymerization temperature was 70° C., and the polymerization time was0.5 hour. Thereafter, a prescribed amount of the solution of the polymer(2a) was sampled and diluted with tetrahydrofuran, and then it wassubjected to GPC measurement. A monomer conversion rate in thispolymerization reaction system was analyzed based on a peak areaobtained from a GPC measured value of a polystyrene solution having aknown concentration. The polymer obtained was reprecipitated and refinedusing hexane. Then, a tetrahydrofuran solution (1 wt %) of the abovepolymer was prepared, and this was allowed to pass through a columnfilled with activated carbon to thereby remove the copper complex byadsorption. Further, this solution was dropwise added to hexane toreprecipitate the polymer, and this was dried (80° C., 6 hours) underreduced pressure. Shown in Table 11 are the analytical results of theconversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2a).

Example 102

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2b), exceptthat a proportion of the compound (64), methyl methacrylate, copper(cuprous bromide:cupric bromide=85:15 (mole ratio)) and L-(−)-sparteinein the solution for polymerization was set to 1:500:0.5:1 in terms of amole ratio in the above order and that a use amount of anisole was setto such an amount that a concentration of methyl methacrylate became 50wt %. In this case, the polymerization temperature was 70° C., and thepolymerization time was 1.0 hour. Then, a prescribed amount of thesolution of the polymer (2b) was sampled and subjected to GPCmeasurement in the same manner as in the case of Example 101.

The polymer obtained was refined in the same manner as in the case ofExample 101. Shown in Table 11 are the analytical results of theconversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2b).

Example 103

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2c), exceptthat a proportion of the compound (64), methyl methacrylate, copper(cuprous bromide:cupric bromide 90:10 (mole ratio)) and L-(−)-sparteinein the solution for polymerization was set to 1:500:0.5:1 in terms of amole ratio in the above order and that a use amount of anisole was setto such an amount that a concentration of methyl methacrylate became 50wt %. In this case, the polymerization temperature was 70° C., and thepolymerization time was 1.0 hour. Then, a prescribed amount of thesolution of the polymer (2c) was sampled and subjected to GPCmeasurement in the same manner as in the case of Example 101.

The polymer obtained was refined in the same manner as in the case ofExample 101. Shown in Table 11 are the analytical results of theconversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2c).

Example 104

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2d), exceptthat a proportion of the compound (64), methyl methacrylate, cuprousbromide and L-(−)-sparteine in the solution for polymerization was setto 1:500:2:4 in terms of a mole ratio in the above order and that a useamount of anisole was set to such an amount that a concentration ofmethyl methacrylate became 50 wt %. In this case, the polymerizationtemperature was 70° C., and the polymerization time was 0.5 hour. Then,a prescribed amount of the solution of the polymer (2d) was sampled andsubjected to GPC measurement in the same manner as in the case ofExample 101. The polymer obtained was refined in the same manner as inthe case of Example 101. Shown in Table 11 are the analytical results ofthe conversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2d).

Example 105

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2e), exceptthat a proportion of the compound (64), methyl methacrylate, cuprousbromide and L-(−)-sparteine in the solution for polymerization was setto 1:500:1:2 in terms of a mole ratio in the above order and that a useamount of anisole was set to such an amount that a concentration ofmethyl methacrylate became 50 wt %. In this case, the polymerizationtemperature was 70° C., and the polymerization time was 0.5 hour. Then,the respective polymers were refined in the same manner as in the caseof Example 101. Shown in Table 11 are the analytical results of a numberaverage molecular weight and a molecular weight distribution of thepolymer (2e). In this case, the value of the conversion rate was notobtained and therefore a theoretical number average molecular weight ofthe polymer (2e) could not be obtained.

Example 106

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2f), exceptthat a proportion of the compound (64), methyl methacrylate, cuprousbromide and L-(−)-sparteine in the solution for polymerization was setto 1:500:0.5:1 in terms of a mole ratio in the above order and that ause amount of anisole was set to such an amount that a concentration ofmethyl methacrylate became 50 wt %. In this case, the polymerizationtemperature was 70° C., and the polymerization time was 0.5 hour. Then,a prescribed amount of the solution of the polymer (2f) was sampled andsubjected to GPC measurement in the same manner as in the case ofExample 101. The polymer obtained was refined in the same manner as inthe case of Example 101. Shown in Table 11 are the analytical results ofthe conversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2f).

Example 107

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2g), exceptthat a proportion of the compound (64), methyl methacrylate, cuprousbromide and L-(−)-sparteine in the solution for polymerization was setto 1:500:0.25:0.50 in terms of a mole ratio in the above order and thata use amount of anisole was set to such an amount that a concentrationof methyl methacrylate became 50 wt %. In this case, the polymerizationtemperature was 70° C., and the polymerization time was 0.6 hour. Then,a prescribed amount of the solution of the polymer (2g) was sampled andsubjected to GPC measurement in the same manner as in the case ofExample 101. The polymer obtained was refined in the same manner as inthe case of Example 101. Shown in Table 11 are the analytical results ofthe conversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2g).

Example 108

Polymerization was carried out in the same manner as in the case ofExample 101 to obtain a brown viscous solution of a polymer (2h), exceptthat a proportion of the compound (64), methyl methacrylate, cuprousbromide and L-(−)-sparteine in the solution for polymerization was setto 1:500:1:2 in terms of a mole ratio in the above order and that a useamount of anisole was set to such an amount that a concentration ofmethyl methacrylate became 50 wt %. In this case, the polymerizationtemperature was 70° C., and the polymerization time was 3.0 hours. Then,a prescribed amount of the solution of the polymer (2h) was sampled andsubjected to GPC measurement in the same manner as in the case ofExample 101. The polymer obtained was refined in the same manner as inthe case of Example 101. Shown in Table 11 are the analytical results ofthe conversion rate and a theoretical number average molecular weight, anumber average molecular weight and a molecular weight distribution ofthe polymer (2h).

TABLE 11 Polymerization Mn Mn Molecular weight Example Example timeConversion teoretical measured distribution No. No. (hr) (mol-%) valuevalue (Mw/Mn) 101 2a 0.5 11.4 6,900 4,500 1.08 102 2b 1.0 4.55 3,4004,700 1.09 103 2c 1.0 6.23 4,300 6,300 1.12 104 2d 0.5 8.64 5,500 6,3001.12 105 2e 0.5 — — 7,100 1.12 106 2f 0.5 8.14 5,200 8,000 1.13 107 2g0.6 14.9 8,600 8,500 1.20 108 2h 3.0 44.0 23,200  28,000 1.14

Polymers can be obtained by the methods according to the examplesdescribed above using the compounds (65) to (69) in place of thecompound (64).

Example 109 Preparation of Solution for Polymerization

Cuprous bromide was introduced into a heat resistant glass-made ampul ina draft which was cut off from a UV ray, and a compound (72)/methylmethacrylate/L-(−)-sparteine/anisole solution was further added theretoand quickly cooled using liquid nitrogen. Then, freezing vacuumdeaeration (pressure: 1.0 Pa) was carried out three times by means of avacuum device equipped with an oil-sealed rotary pump, and the ampul wasquickly sealed by means of a hand burner while maintaining a state ofvacuum. In this case, a proportion of the compound (72), methylmethacrylate, cuprous bromide and L-(−)-sparteine in the above solutionfor polymerization was set to 1:300:1:2 in terms of a mole ratio in theabove order, and a use amount of anisole was set to such an amount thata concentration of methyl methacrylate became 50 wt %.

<Polymerization>

The sealed heat resistant glass-made ampul was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (3a). In this case, thepolymerization temperature was 70° C., and the polymerization time was0.5 hour. A monomer conversion rate in this polymerization reactionsystem was determined from the relation of a proton ratio ofsubstituents in the respective monomer and polymer by diluting thesolution of the polymer (3a) with deuterated chloroform and thensubjecting the solution to ¹H-NMR measurement. The polymer obtained wasreprecipitated and refined using hexane. Then, a tetrahydrofuransolution (1 wt %) of the above polymer was prepared, and this wasallowed to pass through a column filled with activated carbon to therebyremove the copper complex by adsorption. Further, this solution wasdropwise added to hexane to reprecipitate the polymer, and this wasdried (80° C., 6 hours) under reduced pressure. Shown in Table 12 arethe analytical results of the conversion rate and a theoretical numberaverage molecular weight, a number average molecular weight and amolecular weight distribution of the polymer (3a).

Examples 110 to 115

Polymerization was carried out in the same manner as in Example 109 toobtain the respective brown viscous solutions of a polymer (3b) to apolymer (3g), except that the polymerization time was changed as shownin Table 12. Then, the monomer conversion rates were determined in thesame manner as in the case of Example 109, and the respective polymerswere refined in the same manner as in the case of Example 109. Shown inTable 12 are the analytical results of the conversion ratescorresponding to the respective polymers and the respective theoreticalnumber average molecular weights, number average molecular weights andmolecular weight distributions of the polymer (3b) to the polymer (3g).

TABLE 12 Polymerization Mn Mn Molecular weight Example Example timeConversion teoretical measured distribution No. No. (hr) (mol-%) valuevalue (Mw/Mn) 109 3a 0.5 13.0 5,100 7,600 1.13 110 3b 1.0 27.1 9,30011,800 1.14 111 3c 1.5 35.7 11,900 14,600 1.15 112 3d 2.0 44.1 14,40017,900 1.15 113 3e 3.0 55.8 17,900 21,500 1.15 114 3f 4.0 65.5 20,80025,400 1.17 115 3g 5.0 73.7 23,300 28,800 1.16

Polymers can be obtained by the methods according to the examplesdescribed above using the compounds (73) to (77) in place of thecompound (72).

Example 116 Preparation of Solution for Polymerization

Cuprous bromide was introduced into a heat resistant glass-made ampul ina draft which was cut off from a UV ray, and a compound (72)/methylmethacrylate/L-(−)-sparteine/anisole solution was further added theretoand quickly cooled using liquid nitrogen. Then, freezing vacuumdeaeration (pressure: 1.0 Pa) was carried out three times by means of avacuum device equipped with an oil-sealed rotary pump, and the ampul wasquickly sealed by means of a hand burner while maintaining a state ofvacuum. In this case, a proportion of the compound (72), methylmethacrylate, cuprous bromide and L-(−)-sparteine in the above solutionfor polymerization was set to 1:150:1:2 in terms of a mole ratio in theabove order, and a use amount of anisole was set to such an amount thata concentration of methyl methacrylate became 50 wt %.

<Polymerization>

The sealed heat resistant glass-made ampul was set in a constanttemperature shaking bath, and polymerization was carried out to obtain abrown viscous solution of a polymer (4a). In this case, thepolymerization temperature was 70° C., and the polymerization time was0.5 hour. A monomer conversion rate in this polymerization reactionsystem was determined from the relation of a proton ratio ofsubstituents in the respective monomer and polymer by diluting thesolution of the polymer (4a) with deuterated chloroform and thensubjecting the solution to ¹H-NMR measurement. The polymer obtained wasreprecipitated and refined using hexane. Then, a tetrahydrofuransolution (1 wt %) of the above polymer was prepared, and this wasallowed to pass through a column filled with activated carbon to therebyremove the copper complex by adsorption. Further, this solution wasdropwise added to hexane to reprecipitate the polymer, and this wasdried (80° C., 6 hours) under reduced pressure. Shown in Table 13 arethe analytical results of the conversion rate and a theoretical numberaverage molecular weight, a number average molecular weight and amolecular weight distribution of the polymer (4a).

Examples 117 to 122

Polymerization was carried out in the same manner as in Example 116 toobtain the respective brown viscous solutions of a polymer (4b) to apolymer (4g), except that the polymerization time was changed as shownin Table 13. Then, the monomer conversion rates were determined in thesame manner as in the case of Example 116, and the respective polymerswere refined in the same manner as in the case of Example 116. Shown inTable 13 are the analytical results of the conversion ratescorresponding to the respective polymers and the respective theoreticalnumber average molecular weights, number average molecular weights andmolecular weight distributions of the polymer (4b) to the polymer (4g).

TABLE 13 Polymerization Mn Mn Molecular weight Example Example timeConversion teoretical measured distribution No. No. (hr) (mol-%) valuevalue (Mw/Mn) 116 4a 0.25 5.3 2,000 3,800 1.07 117 4b 0.50 16.8 3,7006,200 1.10 118 4c 1.00 39.5 7,100 10,900 1.14 119 4d 1.50 54.1 9,30011,800 1.15 120 4e 2.00 61.9 10,500 13,200 1.15 121 4f 2.50 66.4 11,10013,900 1.16 122 4g 3.00 76.4 12,600 15,400 1.18

Polymers can be obtained by the methods according to the examplesdescribed above using the compounds (73) to (77) in place of thecompound (72).

Example 123 Preparation of Solution for Polymerization

Cuprous chloride was introduced into a Schlenk tube substituted withargon in a draft which was cut off from a UV ray, and a compound(70)/methylmethacrylate/4,4′-di(5-nonyl)-2,2′-bipyridine/dimethylformamide solutionwas further added thereto and quickly cooled using liquid nitrogen.Then, freezing vacuum deaeration (pressure: 1.0 Pa) was carried outthree times by means of a vacuum device equipped with an oil-sealedrotary pump, and argon was finally introduced thereinto. In this case, aproportion of the compound (70), methyl methacrylate, cuprous chlorideand 4,4′-di(5-nonyl)-2,2′-bipyridine in the above solution forpolymerization was set to 1:399:1:2 in terms of a mole ratio in theabove order, and a use amount of dimethylformamide was set to such anamount that a concentration of methyl methacrylate became 50 wt %.

<Polymerization>

The Schlenk tube described above was set in a constant temperatureshaking bath, and polymerization was carried out to obtain a brownviscous solution of a polymer (5a). In this case, the polymerizationtemperature was 70° C., and the polymerization time was 0.5 hour. Then,a prescribed amount of the solution of the polymer (5a) was sampled andsubjected to GPC measurement after diluted with tetrahydrofuran. Amonomer conversion rate in this polymerization reaction system wasdetermined from the relation of a proton ratio of substituents in therespective monomer and polymer by diluting the solution of the polymer(5a) with deuterated chloroform and then subjecting the solution to¹H-NMR measurement. The polymer obtained was reprecipitated and refinedusing hexane. Then, a tetrahydrofuran solution (1 wt %) of the abovepolymer was prepared, and this was allowed to pass through a columnfilled with activated carbon to thereby remove the copper complex byadsorption. Further, this solution was dropwise added to hexane toreprecipitate the polymer, and this was dried (80° C., 6 hours) underreduced pressure. Shown in Table 14 are the analytical results of atheoretical number average molecular weight, a number average molecularweight and a molecular weight distribution of the polymer (5a), and adifference was apparently observed between the theoretical values of thenumber average molecular weights and the measured values thereof.

<Analysis of Theoretical Number Average Molecular Weight of Graft Chain>

A theoretical number average molecular weight of the graft chain wascalculated according to the following equation assuming that an esterbond which was an initiating end in the polymerization was cut off byhydrolysis brought about by hydrofluoric acid treatment and that allterminating ends in the polymerization had become Br. The resultsthereof are shown in Table 14-2.

<Calculating Equation>

Theoretical Mn of graft chain=(monomer consumption rate (mole%)/100)×MW_(M)×(mole ratio of vinyl base monomer to α-bromoestergroup)+MW₁

<Parameters Used for Calculation>

MW_(M)=100 (methyl methacrylate)

Mole ratio of vinyl base monomer to α-bromoester group=300

MW₁=167.01 (BrC(CH₃)₂CO₂H)

<Molecular Weight Measurement of Graft Chain>

The polymer (5a) (15.5 mg) was dissolved in toluene (2.0 ml) in apolypropylene-made microtube (10 ml) into which a rotator wasintroduced. A mixture of a phase transfer catalyst(trioctylmethylammonium chloride, 20 mg), hydrofluoric acid (1.0 ml) andwater (3.0 ml) was added thereto, and the solution was stirred at 25° C.for 12 hours by means of a magnetic stirrer. After finishing thereaction, neutralizing treatment by sodium hydrogencarbonate was carriedout, and then a prescribed amount of the supernatant organic layer wassampled and subjected to GPC measurement after diluted withtetrahydrofuran.

Results obtained by subjecting this polymer to GPC measurement are shownin Table 14-2, and it was found that they were almost consistent withtheoretical Mn of the graft chains derived from the calculating equationdescribed above.

Accordingly, it was indicated that in the polymers before subjected tohydrofluoric acid treatment, the polymers themselves were aggregated bystrong interaction between silsesquioxanes in tetrahydrofuran.

Examples 124 to 130

Polymerization was carried out in the same manner as in Example 123 toobtain the respective brown viscous solutions of a polymer (5b) to apolymer (5h), except that the polymerization time was changed as shownin Table 14-1. Then, a monomer conversion rate, a theoretical numberaverage molecular weight, a number average molecular weight and amolecular weight distribution in the respective polymers were determinedin the same manner as in the case of Example 123, and the resultsthereof are shown Table 14-1. In all polymers, a difference wasapparently observed between the theoretical values of the number averagemolecular weights and the measured values thereof.

Then, calculation of a theoretical number average molecular weight ofthe graft chains, hydrofluoric acid treatment of the polymers andanalysis of a number average molecular weight and a molecular weightdistribution of the graft chains were carried out in the respectivepolymers in the same manner as in Example 123, and the results thereofare shown Table 14-1. It was found that measured Mn of the graft chainswas almost consistent with theoretical MN thereof in all polymers.Accordingly, it was indicated that in the polymers obtained in thepresent examples, the polymers themselves were aggregated by stronginteraction between silsesquioxanes in tetrahydrofuran.

TABLE 14-1 Polymerization Mn Mn Molecular weight Example Example timeConversion teoretical measured distribution No. No. (hr) (mol-%) valuevalue (Mw/Mn) 123 5a 0.5 12.1 6,100 18,300 1.15 124 5b 1.0 22.2 10,20022,700 1.23 125 5c 1.5 27.4 12,200 27,400 1.26 126 5d 2.0 31.4 13,80030,200 1.22 127 5e 3.0 38.4 16,600 34,900 1.23 128 5f 4.0 44.3 19,00037,800 1.27 129 5g 5.0 47.9 20,400 40,100 1.26 130 5h 6.0 51.6 21,90043,700 1.32

TABLE 14-2 (data on graft chain) Polymerization Mn Molecular weightExample Example time measured distribution No. No. (hr) value (Mw/Mn)123 5a 5,000 7,500 1.42 124 5b 9,000 11,300 1.29 125 5c 11,100 13,5001.28 126 5d 12,700 15,300 1.26 127 5e 15,500 18,300 1.24 128 5f 17,80021,400 1.20 129 5g 19,300 23,000 1.20 130 5h 20,800 24,800 1.19

INDUSTRIAL APPLICABILITY

The silicon compound provided by the present invention is asilsesquioxane derivative having an excellent living polymerizableradical polymerization-initiating function. The silicon compound of thepresent invention shows an excellent living radical polymerizabilityparticularly to styrene derivatives. For example, it is possible toinitiate polymerization of a styrene base monomer by the siliconcompound of the present invention to form a styrene base polymer withone point in the silsesquioxane structure of the present invention beingused as a starting point. In the polymer thus obtained having an organicgroup of a silsesquioxane structure at an end, it is possible as well topositively make use of interaction between the organic groups of thesilsesquioxane structure thereof. This makes it possible not only toobtain an organic-inorganic composite material having a distinctstructure but also to control the structure of the above polymer as amolecular aggregate. Further, the silicon compound of the presentinvention has characteristics other than the function of apolymerization initiator. For example, α-haloester has a strongelectrophilicity, and therefore reaction of the silicon compound of thepresent invention with nucleophilic reagents makes it possible tosynthesize various silsesquioxane derivatives corresponding to thenucleophilic reagents. Accordingly, the silicon compound of the presentinvention is also useful as an intermediate in organic synthesis.

1-24. (canceled)
 25. A production process for a silicon compoundrepresented by Formula (6), characterized by reacting a compoundrepresented by Formula (4) with a compound represented by Formula (5):

wherein all R¹²'s are the same group selected from alkyl having a carbonatom number of 1 to 8 in which optional hydrogens may be substitutedwith fluorine and in which optional —CH₂— may be substituted with —O—,—CH═CH—, cycloalkylene or cycloalkenylene, phenyl in which optionalhydrogens may be substituted with halogen, methyl or methoxy,non-substituted naphthyl and phenylalkyl constituted from phenyl inwhich optional hydrogens may be substituted with fluorine, alkyl havinga carbon atom number of 1 to 4, vinyl or methoxy and alkylene which hasa carbon atom number of 1 to 8 and in which optional —CH₂— may besubstituted with —O—; Z¹ is alkylene having a carbon atom number of 1 to20 or alkenylene having a carbon atom number of 3 to 8, and in thesealkylene and alkenylene, optional —CH₂— may be substituted with —O—;

wherein both of X¹ and X² are halogens and may be the same or different;R² is alkyl having a carbon atom number of 1 to 20, aryl having a carbonatom number of 6 to 20 or aralkyl having a carbon atom number of 7 to20; and R³ is hydrogen, alkyl having a carbon atom number of 1 to 20,aryl having a carbon atom number of 6 to 20 or aralkyl having a carbonatom number of 7 to 20;

wherein R¹² and Z¹ each have the same meanings as those of these codesin Formula (4), and R², R³ and X¹ each have the same meanings as thoseof these codes in Formula (5). 26-32. (canceled)